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WO2013073714A1 - Infrared ray shielding composition, infrared ray shielding film, pattern forming method and solid-state imaging device - Google Patents

Infrared ray shielding composition, infrared ray shielding film, pattern forming method and solid-state imaging device Download PDF

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Publication number
WO2013073714A1
WO2013073714A1 PCT/JP2012/080408 JP2012080408W WO2013073714A1 WO 2013073714 A1 WO2013073714 A1 WO 2013073714A1 JP 2012080408 W JP2012080408 W JP 2012080408W WO 2013073714 A1 WO2013073714 A1 WO 2013073714A1
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Prior art keywords
group
infrared ray
ray shielding
compound
shielding composition
Prior art date
Application number
PCT/JP2012/080408
Other languages
French (fr)
Inventor
Yoshinori Tamada
Naotsugu Muro
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Fujifilm Corporation
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Publication of WO2013073714A1 publication Critical patent/WO2013073714A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F39/00—Integrated devices, or assemblies of multiple devices, comprising at least one element covered by group H10F30/00, e.g. radiation detectors comprising photodiode arrays
    • H10F39/80—Constructional details of image sensors
    • H10F39/804—Containers or encapsulations
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F39/00—Integrated devices, or assemblies of multiple devices, comprising at least one element covered by group H10F30/00, e.g. radiation detectors comprising photodiode arrays
    • H10F39/80—Constructional details of image sensors
    • H10F39/805—Coatings
    • H10F39/8057—Optical shielding
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/035—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyurethanes
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0384—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the main chain of the photopolymer
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

Definitions

  • the present invention relates to an infrared ray shielding composition, an infrared ray shielding film, a pattern forming method and a solid-state imaging device, Particularly, it relates to an infrared ray shielding composition suitably used for forming a solder resist, an infrared ray shielding film, a pattern forming method and a solid-state imaging device.
  • a method of forming a permanent pattern for example, a solder resist
  • a photosensitive layer is formed on a silicon wafer on which a permanent pattern is formed, a silicon wafer having wiring thereon or a base material, for example, a copper clad laminate, and the photosensitive layer of the stack is exposed to light, after the exposure the photosensitive layer is developed to form a pattern and then subjected to a curing treatment or the like, thereby forming the permanent pattern.
  • the formation of permanent pattern is also applied to a package substrate interposed between a semiconductor chip and a printed board.
  • the package substrate in recent years, higher density packaging is required, and decrease in the wiring pitch and increase in the strength, improvement in the insulating property, decrease in the film thickness and the like of a solder resist layer are proceeding. Also, reduction in the via diameter, increase in the exposure sensitivity and from the standpoint of mounting, a rectangular pattern profile by development are required.
  • a solid-state imaging device used in a cellular phone, a digital camera, a digital video, a monitoring camera or the like is a photoelectric conversion device having an integrated circuit formed using the production technique of a semiconductor device.
  • the solid-state imaging device is required to be more downsized.
  • JP-A-2009-194396 the term "JP-A” as used herein means an "unexamined published Japanese patent application”
  • the downsizing can be realized by polishing the silicon wafer to decrease the thickness thereof, but due to the decrease in the thickness of silicon wafer, light having a wavelength of 800 nm or more is liable to be transmitted, although the light shielding property of light having a wavelength of 800 nm or less is maintained.
  • the solid-state imaging device has a configuration in that a color filter and a lens are provided adjacent to one side of a photodiode, an infrared cut filter is present in the vicinity of the color filter or lens to block light having a wavelength from 800 to 1,200 nm, and a metal wiring, a solder resist and the like are present on the opposite side of the color filter.
  • the space between the metal wirings is filled with the solder resist in many cases, but there is a problem in that infrared light, for example, leakage light intruding into the inside of a cellular phone, a digital camera or the like cannot be blocked by the solder resist.
  • the composition preferably exhibits photosensitivity and has a photolithography performance enabling patterning by exposure.
  • the light shielding photosensitive composition having a photolithography performance includes a black resist containing carbon black used for the formation of an LCD color filter.
  • the carbon black has a high light shielding property in the visible region but exhibits a low light shielding property in the infrared region and when it is attempted to apply such a black resist as a solder resist, if carbon black is added in an amount large enough to ensure the required light shielding property in the infrared region, this causes a problem in that the light shielding property in the visible region becomes excessively high, light having a shorter wavelength than the visible region, which is usually used at the exposure by a high-pressure mercury lamp, KrF, ArF or the like in the image formation, is also blocked so that the photocurability is not sufficiently obtained and excellent pattern cannot be obtained through a development step using an alkali developer.
  • an infrared ray shielding layer is separately provided after forming a solder resist by a coating method, in the formation of solder resist and the formation of infrared ray shielding layer, steps, for example, coating, exposure, development and post-heating must be performed plural times to cause a cumbersome process and a rise in the cost and thus, improvements are desired.
  • a black solder resist composition containing a black coloring agent, a coloring agent other than black and a polyfunctional epoxy compound has been proposed (see, for example, JP-A-2008-257045).
  • the composition is characterized in that the content of the black coloring agent is kept low by using a coloring agent other than black in combination and is practically insufficient from the standpoint of light shielding property in the infrared region.
  • an alignment mark of a convex form is often provided at the predetermined position on the surface on the metal wiring and solder resist side (that is, the surface opposite the color filter or lens) of a semiconductor substrate of a solid-state imaging device.
  • an infrared ray shielding composition having a high light shielding property in the infrared region, high light transparency in the visible region and high exposure sensitivity and capable of forming a pattern of high rectangularity by development is demanded at present.
  • a technique of using a layer containing an inorganic near infrared ray absorbing agent as a near infrared ray absorbing layer for an image display device is disclosed in JP-A-2009-205029 and, for example, a coating solution for forming near infrared ray absorbing layer containing a polymerizable compound, a polymerization initiator and a near infrared ray absorbing agent is disclosed in the example thereof, but an infrared ray shielding composition capable of forming a solder resist layer in which the occurrence of cracking is restrained and which exhibits a high adhesion property to a substrate so as to hardly cause the peeling is not described. Thus, such an infrared ray shielding composition is demanded at present.
  • an object of the invention is to provide an infrared ray shielding composition having a high light shielding property in the infrared region and high light transparency in the visible region and being capable of forming an infrared ray shielding film in which the occurrence of cracking is restrained and which exhibits a high adhesion property to a substrate and high exposure sensitivity, and an infrared ray shielding film, a pattern forming method and a solid-state imaging device each using the composition.
  • An infrared ray shielding composition containing a fine particle of tungsten oxide containing an alkali metal, a triazine polymerization initiator and a polymerizable compound.
  • a halogen-substituted hydrocarbon group a hydrogen atom, a halogen atom, a dialkylamino group, an alkyl group, an alkoxy group or a cyano group
  • Y 1 which is not present when 1 is 0, represents an ethenylene group or an -NH- group when 1 is 1
  • B 1 and B 2 each independently represents an aromatic ring group which may have a substituent
  • 1 and m each independently represents any integer selected from 0, 1 and 2.
  • aromatic ring constituting the aromatic ring group for B or B in formula (T) is a benzene ring.
  • M represents an alkali metal
  • W represents tungsten
  • O represents oxygen
  • a photosensitive layer which is formed from the infrared ray shielding composition as described in any one of (1) to (10) above.
  • a solid-state imaging device comprising a solid-state imaging device substrate having an imaging device unit formed on one surface thereof, and the infrared ray shielding film as described in (12) above provided on the other surface side of the solid-state imaging device substrate.
  • a pattern forming method comprising, in this order, a step of forming the photosensitive layer as described in (11) above, a step of pattern-exposing the photosensitive layer to cure an exposed area, and a step of removing an unexposed area by alkali development to form a pattern.
  • an infrared ray shielding composition having a high light shielding property in the infrared region and high light transparency in the visible region and being capable of forming an infrared ray shielding film in which the occurrence of cracking is restrained and which exhibits a high adhesion property to a substrate and high exposure sensitivity, and an infrared ray shielding film, a pattern forming method and a solid-state imaging device each using the composition can be provided.
  • Fig. 1 is a schematic cross-sectional view showing the configuration of a camera module equipped with the solid-state imaging device according to an embodiment of the invention.
  • Fig. 2 is a schematic cross-sectional view showing the solid-state imaging device according to an embodiment of invention.
  • Fig. 3 is a plan view showing one example of a wafer-level lens array.
  • Fig. 4 is a cross-sectional view along the line A-A in Fig. 3.
  • an alkyl group includes not only an alkyl group having no substituent (an unsubstituted alkyl group) but also an alkyl group having a substituent (a substituted alkyl group).
  • the term "(meth)acrylate” represents acrylate and methacrylate
  • the term “(meth)acryl” represents acryl and methacryl
  • the term “(meth)acryloyl” represents acryloyl and methacryloyl.
  • the term “monomeric compound” has the same meaning as the term “monomer”.
  • the monomeric compound in the invention is distinguished from an oligomer and a polymer and means a compound having a weight average molecular weight of 2,000 or less.
  • a polymerizable compound means a compound having a polymerizable group and may be a monomeric compound or a polymer.
  • the polymerizable group means a group involved in a polymerization reaction.
  • the infrared ray shielding composition according to the invention contains a fine particle of tungsten oxide containing an alkali metal, a triazine polymerization initiator and a polymerizable compound, and may contain, if desired, a binder (preferably, an alkali-soluble binder), an infrared ray blocking agent other than the fine particle of tungsten oxide described above, a dispersing agent, an ultraviolet absorbing agent, a sensitizer, a crosslinking agent, a curing accelerator, a filler, an elastomer, a surfactant and other components.
  • a binder preferably, an alkali-soluble binder
  • an infrared ray blocking agent other than the fine particle of tungsten oxide described above a dispersing agent, an ultraviolet absorbing agent, a sensitizer, a crosslinking agent, a curing accelerator, a filler, an elastomer, a surfactant and other components.
  • the inventors have found that by further incorporating a triazine polymerization initiator into an infrared ray shielding composition having a high light shielding property in the infrared region and high light transparency in the visible region obtained by incorporating a fine particle of tungsten oxide containing an alkali metal, an infrared ray shielding film in which the occurrence of cracking is restrained and which exhibits a high adhesion property to a substrate and high exposure sensitivity can be formed, though the reason is not clear.
  • the invention has been made based on this finding.
  • the infrared ray shielding composition according to the invention is a polymerizable composition, for example, a negative polymerizable composition and typically a negative polymerizable composition.
  • a polymerizable composition for example, a negative polymerizable composition and typically a negative polymerizable composition.
  • the configuration of the composition is described below.
  • the triazine polymerization initiator for use in the infrared ray shielding composition according to the invention is not particularly restricted as long as it has a function of initiating polymerization of the polymerizable compound by either light or heat, or both, and it can be appropriately selected depending to the purpose, but it is preferably a photopolymerization initiator.
  • a compound having photosensitivity to light from an ultraviolet region to a visible region is preferred.
  • an initiator capable of decomposing from 150 to 250°C is preferred.
  • the triazine polymerization initiator is more suitably an s-triazine derivative in which an s-triazine ring has at least one substituent, for example, a halogen atom or a halogen-substituted hydrocarbon group.
  • the triazine polymerization initiator is preferably represented by formula (T)
  • the halogen atom for X or X or the halogen atom in the halogen-substituted hydrocarbon group includes, for example, a chlorine atom, a fluorine atom and a bromine atom, and is preferably a chlorine atom.
  • the halogen-substituted hydrocarbon group includes, for example, a halogen-substituted alkyl group and a halogen-substituted cycloalkyl group.
  • the halogen-substituted alkyl group is preferably a halogen-substituted alkyl group having from 1 to 5 carbon atoms.
  • the halogen-substituted cycloalkyl group is preferably a halogen-substituted cycloalkyl group having from 3 to 10 carbon atoms.
  • the alkyl group for X or X , the alkyl moiety of the dialkylamino group or the alkyl moiety of the alkoxy group is preferably an alkyl group having from 1 to 5 carbon atom, and includes, for example, a methyl group, an ethyl group, a propyl group and a butyl group.
  • X 1 and X 2 each represents more preferably a halogen-substituted hydrocarbon group, and still more preferably a halogen-substituted alkyl group.
  • the halogen-substituted alkyl group is more preferably a monohalomethyl group, a dihalomethyl group or a trihalomethyl group, and still more preferably a trihalomethyl group.
  • Y 1 which is not present when 1 is 0, represents an ethenylene group or an -NH- group when 1 is 1, and is preferably an ethenylene group.
  • B and B each independently represents an aromatic ring group which may have a substituent, and is preferably an aromatic ring group having from 5 to 15 carbon atoms.
  • the aromatic ring group may be a heterocyclic group.
  • the substituent include a halogen atom, a cyano group, an alkyl group, an alkoxy group, a hydroxy group, an alkyl ester group, an alkylamido group and an aryl group (preferably an aryl group having from 6 to 10 carbon atoms).
  • the aromatic ring constituting the aromatic ring group includes, for example, a benzene ring, a coumalin ring and a benzodioxole ring, and is preferably a benzene ring.
  • B is preferably a 1 ,4-phenylene group, and B is preferably a phenyl group.
  • 1 and m each independently represents any integer selected from 0, 1 and 2.
  • triazine polymerization initiator examples include
  • 2-methyl-4,6-bis(tribromomethyl)-s-triazine 2-methoxy-4,6-bis(tribromomethyl)-s-triazine.
  • 2-biphenyl-4,6-bis(trichloromethyl)-s-triazine 2-biphenyl-4,6-bis(trichloromethyl)-s-triazine
  • 2-biphenyl-4,6-bis(trichloromethyl)-s-triazine is particularly preferred.
  • the triazine polymerization initiators may be used individually or in combination of two or more thereof.
  • the content of the triazine polymerization initiator is preferably from 0.01 to 30% by weight, more preferably from 0.1 to 20% by weight, particularly preferably from 0.1 to 15% by weight, based on the total solid content of the infrared ray shielding composition according to the invention.
  • the infrared ray shielding composition according to the invention may contain a polymerization initiator (hereinafter, also simply referred to as a "combination polymerization initiator”) other than the triazine polymerization initiator described above.
  • a polymerization initiator hereinafter, also simply referred to as a "combination polymerization initiator”
  • the combination polymerization initiator is not particularly restricted as long as it has an ability of initiating polymerization of the polymerizable compound described above and may be appropriately selected from known polymerization initiators. For example, those having radiation sensitivity to light in the region from ultraviolet to visible are preferred.
  • the initiator may also be an activator capable of causing a certain action with a photoexcited sensitizer to generate an active radical or an initiator capable of initiating cationic polymerization depending on the kind of the monomer.
  • the combination polymerization initiator preferably contains at least one kind of compound having a molecular extinction coefficient of at least about 50 in the range from about 300 to about 800 nm (more preferably from 330 to 500 nm).
  • the combination polymerization initiator examples include a halogenated hydrocarbon derivative (for example, a compound having an oxadiazole skeleton), an acylphosphine compound, for example, an acylphosphine oxide, a hexaarylbiimidazole, an oxime compound, for example, an oxime derivative, an organic peroxide, a thio compound, a ketone compound, an aromatic onium salt, a ketoxime ether, an aminoacetophenone compound and a hydroxyacetophenone.
  • a halogenated hydrocarbon derivative for example, a compound having an oxadiazole skeleton
  • an acylphosphine compound for example, an acylphosphine oxide, a hexaarylbiimidazole
  • an oxime compound for example, an oxime derivative, an organic peroxide, a thio compound, a ketone compound, an aromatic onium salt, a ketoxime
  • the compound having an oxadiazole skeleton includes, for example, compounds described in U. S . Patent 4,212,976. Specific examples thereof include
  • combination polymerization initiator examples include an acridine derivative (e.g., 9-phenylacridine, l,7-bis(9,9'-acridinyl)heptane),
  • N-phenylglycine N-phenylglycine, a polyhalogen compound (e.g., carbon tetrabromide, phenyl tribromomethyl sulfone or phenyl trichloromethyl ketone), a coumarin (e.g.,
  • an acylphosphine oxide e.g., bis(2,4,6-tiimemylbenzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphenylphosphine oxide or Lucirin TPO
  • a metallocene e.g., bis(2,4,6-tiimemylbenzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphenylphosphine oxide or Lucirin TPO
  • a metallocene e.g.,
  • ketone compound examples include benzophenone, 2-methylbenzophenone,
  • 2-ethoxycarbonylbenzophenone benzophenone tetracarboxylic acid or a tetramethyl ester thereof, a 4,4'-bis(dialkylamino)benzophenone (e.g., 4,4'-bis(dimethylamino)benzophenone,
  • 4,4'-bis(dihydroxyethylamino)benzophenone 4-methoxy-4'-dimethylaminobenzophenone, 4,4'-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylaminoacetophenone, benzyl, anthraquinone, 2-tert-butylanthraquinone, 2-methylanthraquinone, phenanthraquinone, xanthone, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, fluorenone,
  • 2-hydroxy-2-methyl-[4-(l-methylvinyl)phenyl]propanol oligomer benzoin, a benzoin ether (e.g., benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin phenyl ether, benzyl dimethyl ketal), acridone, chloroacridone, N-methylacridone, N-butylacridone and N-butyl-chloroacridone.
  • a benzoin ether e.g., benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin phenyl ether, benzyl dimethyl ketal
  • acridone chloroacridone, N-methylacridone, N-butylacridone and N-but
  • a hydroxyacetophenone compound, an aminoacetophenone compound and an acylphosphine compound may also be suitably used as the combination polymerization initiator. More specifically, for example, an aminoacetophenone initiator described in JP-A- 10-291969 and an acylphosphine oxide initiator described in Japanese Patent 4225898 may be used.
  • IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959 and IRGACURE-127 may be used.
  • aminoacetophenone initiator commercially available products of IRGACURE-907, IRGACURE-369 and IRGACURE-379 (produced by BASF) may be used.
  • aminoacetophenone initiator compounds in which the absorption wavelength matches a light source having a long wavelength, for example, 365 nm or 405 nm described in JP-A-2009-191179 may be also used.
  • acylphosphine initiator commercially available products of IRGACURE-819 and DAROCUR-TPO (produced by BASF) may be used.
  • An oxime compound is also suitably used as the combination polymerization initiator.
  • Specific examples of the oxime initiator used include compounds described in JP-A-2001 -233842, compounds describe in JP-A-2000-80068 and compounds described in JP-A-2006-342166.
  • oxime compound for example, an oxime derivative, which is suitably used as the combination polymerization initiator in the invention, include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3 -one, 2-acetoxyimino- 1 -phenylpropan- 1 -one,
  • Examples of the oxime ester compound include compounds described in J. C. S. Perkin II, pp. 1653-1660 (1979), J. C. S. Perkin II, pp. 156-162 (1979), Journal of Photopolvmer Science and Technology, pp. 202-232 (1995), Journal of Applied Polymer Science, pp. 725-731 (2012) and JP-A-2000-66385, and compounds described in JP-A-2000-80068, JP-T-2004-534797 and JP-A-2006-342166.
  • IRGACURE-OXE01 produced by BASF
  • IRGACURE-OXE02 produced by BASF
  • TR-PBG-304 produced by Changzhou Tronly New Electric Materials Co., Ltd.
  • oxime ester compound other than those described above for example, compounds described in JP-T-2009-519904 where oxime is connected to N-position of carbazole, compounds described in U.S. Patent 7,626,957 where a hetero substituent is introduced into a benzophenone moiety, compounds described in JP-A-2010-15025 and U.S. Patent Application Publication No. 2009-292039 where a nitro group is introduced into a dye moiety, ketoxime compounds described in WO 2009/131189, compounds containing a triazine skeleton and an oxime skeleton in the same molecule described in U.S. Patent 7,556,910, and compounds having an absorption maximum at 405 nm and exhibiting good sensitivity to a g-ray light source described in JP-A-2009-221114 may be also used.
  • cyclic oxime compounds described in JP-A-2007-231000 and JP-A-2007-322744 may be also suitably used.
  • cyclic oxime compounds fused to a carbazole dye described in JP-A-2010-32985 and JP-A-2010-185072 are preferred from the standpoint of high light absorbing property and high sensitivity.
  • compounds having an unsaturated bond at a specific site thereof described in JP-A-2009-242469 can be suitably used because they can achieve high sensitivity by regenerating an active radical from a polymerization inactive radical.
  • oxime compound having a specific substituent described in JP-A-2007-269779 and the oxime compound having a thioaryl group described in JP-A-2009-191061 are exemplified.
  • the combination polymerization initiator which may be used in the infrared ray shielding composition according to the invention is preferably a compound selected from the group consisting of a benzyldimethylketal compound, an a-hydroxyketone compound, an a-aminioketone compound, an acylphosphine compound, a phosphinoxide compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, an onium compound, a benzothiazole compound, a benzophenone compound, an acetophenone compound or a derivative thereof, cyclopentadiene-benzene-iron complex or a salt thereof, a halomethyloxadiazole compound and a 3-aryl-substituted coumarin compound.
  • the content (total content, in case of using two or more) of the combination polymerization initiator contained in the infrared ray shielding composition according to the invention is preferably from 0.001 to 10% by weight, more preferably from 0.01 to 5% by weight, based on the total solid content of the infrared ray shielding composition.
  • the infrared ray shielding composition according to the invention contains a polymerizable compound.
  • the polymerizable compound used may be any compound as long as it is a compound having a functional group capable of undergoing a reaction with at least one of an acid, a radical and heat (in the specification, such a functional group is sometimes referred to as a "polymerizable group") in its molecule, and is preferably a polyfunctional polymerizable compound having a plurality of polymerizable groups in its molecule.
  • Examples of the polymerizable compound having a polymerizable functional group capable of reacting with at least one of an acid, a radical and heat include an ethylenically unsaturated group-containing compound having an ethylenically unsaturated group, for example, an unsaturated ester functional group, an unsaturated amido group, a vinyl ether group or an allyl group, a methylol compound, a bismaleimide compound, a benzocyclobutene compound, a bisallylnadiimide compound and a benzoxazine compound.
  • an ethylenically unsaturated group-containing compound having an ethylenically unsaturated group for example, an unsaturated ester functional group, an unsaturated amido group, a vinyl ether group or an allyl group, a methylol compound, a bismaleimide compound, a benzocyclobutene compound, a bisallylnadiimide compound and a benzo
  • the polymerizable compound which can be preferably used in the invention includes an ordinal radical polymerizable compound and compounds widely known as the compound having an ethylenically unsaturated double bond in the field of art can be used without any particular restriction.
  • the compound has a chemical form, for example, of a monomer, a prepolymer (specifically, a dimer, a trimer or an oligomer), or a mixture thereof or a copolymer thereof.
  • Examples of the monomer and copolymer thereof include an unsaturated carboxylic acid (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid or maleic acid), its ester and amide, and copolymer thereof.
  • an unsaturated carboxylic acid ester, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound and an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound are used.
  • the ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound can exhibit high hydrophobicity in the exposed area and is preferred because a pattern having a desired profile is easily formed by alkali development and also a pattern having high durability is obtained (in particular, when higher durability is required of the solder resist, for example, in the case where the wiring density of the metal wiring covered with the solder resist is high, the effects described above are significant).
  • an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent for example, a hydroxy group, an amino group or a mercapto group with a monofunctional or polyfunctional isocyanate or epoxy
  • a dehydration condensation reaction product of the unsaturated carboxylic acid ester or amide with a monofunctional or polyfunctional carboxylic acid are also suitably used.
  • An addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent for example, an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol
  • a substitution reaction product of an unsaturated carboxylic acid ester or amide having a releasable substituent for example, a halogen group or a tosyloxy group with a monofunctional or polyfunctional alcohol, amine or thiol
  • a compound in which the unsaturated carboxyl acid described above is replaced, for example, with an unsaturated phosphonic acid, styrene or vinyl ether may also be used.
  • the unsaturated carboxylic acid ester is preferably a methacrylic acid ester and examples thereof include tetramethylene glycol dimethacrylate, Methylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis[p-(3-methacryloxy-2-hydroxypropoxy)
  • the unsaturated carboxylic acid ester is also preferably an itaconic acid ester and examples thereof include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate and sorbitol tetraitaconate.
  • the crotonic acid ester include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate and sorbitol tetradicrotonate.
  • Examples of the isocrotonic acid ester include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate and sorbitol tetraisocrotonate.
  • Examples of the maleic acid ester include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate and sorbitol tetramaleate.
  • ester monomer of an aliphatic polyhydric alcohol compound with an unsaturated carboxylic acid include, as the (meth)acrylic acid ester, ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri(acryloyloxypropyl)ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, tricyclodecanedimethanol diacrylate, tricyclodecanedimethanol dimethacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetra
  • esters for example, aliphatic alcohol esters described in JP-B-51-47334 (the term "JP-B” as used herein means an "examined Japanese patent publication") and JP-A-57- 196231, those having an aromatic skeleton described in JP-A-59-5240, JP-A-59-5241 and JP-A-2-226149 and those having an amino group described in JP-A-1-165613 are also suitably used.
  • the ester monomers described above may also be used as a mixture.
  • amide monomer of an aliphatic polyvalent amine compound with an unsaturated carboxylic acid examples include methylene bisacrylamide, methylene bismethacrylamide, 1,6-hexamethylene bisacrylamide, 1,6-hexamethylene bismethacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide and xylylene bismethacrylamide.
  • amide monomer examples include those having a cyclohexylene structure described in JP-B-54-21726.
  • a urethane-based addition-polymerizable compound produced by an addition reaction of an isocyanate with a hydroxy group is also suitable, and specific examples thereof include a vinyl urethane compound having two or more polymerizable vinyl groups per molecule obtained by adding a hydroxy group-containing vinyl monomer represented by formula (E) shown below to a polyisocyanate compound having two or more isocyanate groups per molecule described in JP-B-48-41708.
  • R 4 and R 5 each independently represents H or CH 3 .
  • urethane acrylates described in JP-A-51-37193, JP-B-2-32293 and JP-B-2-16765 and urethane compounds having an ethylene oxide skeleton described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417 and JP-B-62-39418 are also suitable.
  • addition-polymerizable compounds having an amino structure or sulfide structure in the molecule described in JP-A-63-277653, JP-A-63 -260909 and JP-A-1 -105238 are used, an infrared ray shielding composition having very excellent in the photosensitive speed can be obtained.
  • polyfunctional acrylate or methacrylate for example, polyester acrylates described in JP-A-48-64183, JP-B-49-43191 and JP-B-52-30490, and epoxy acrylates obtained by reacting an epoxy resin with (meth)acrylic acid.
  • Other examples also include specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337 and JP-B-1-40336, and vinylphosphonic acid compounds described in JP-A-2-25493.
  • a perfluoroalkyl group-containing structure described in JP-A-61-22048 is suitably used.
  • photocurable monomers and oligomers described in Journal of The Adhesion Society of Japan. Vol. 20, No. 7, pp. 300-308 (1984) may also be used.
  • a radical polymerizable compound when added, from the standpoint of curing sensitivity, a polyfunctional polymerizable compound containing two or more ethylenically unsaturated bonds is preferably used, and it is more preferred to contain three or more ethylenically unsaturated bonds.
  • a compound containing two or more (meth)acrylic acid ester structures is preferred, a compound containing three or more (meth)acrylic acid ester structures is more preferred, and a compound containing four or more (meth)acrylic acid ester structures is most preferred.
  • a compound containing an EO-modified product is preferred, and from the standpoint of curing sensitivity and strength of the exposed area, a compound containing a urethane bond is also preferably used.
  • a compound having an acid group is preferably used.
  • preferred examples of the polymerizable compound for use in the invention include bisphenol A diacrylate, EO-modified bisphenol A diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri(acryloyloxypropyl)ether, trimethylolethane triacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythntol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaaciylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaaciylate, tri(acryloyloxyethyl)isocyanurate, EO-modified pentaerythr
  • U ETHANE OLIGOMER UAS-10 UAB-140 (produced by Sanyo Kokusaku Pulp Co., Ltd.), DPHA-40H (produced by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600 and AI-600 (produced by Kyoeisha Chemical Co., Ltd.) and A-DCP (produced by Shin-Nakamura Chemical Co., Ltd.) are preferred.
  • EO-modified bisphenol A diacrylate pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tri(acryloyloxyethyl)isocyanurate, EO-modified pentaerythritol tetraacrylate and EO-modified dipentaerythritol hexaacrylate are more preferred, and as the commercially available products, DPHA-40H (produced by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600 and AI-600 (produced by Kyoeisha Chemical Co., Ltd.) and A-DCP (produced by Shin-Nakamura Chemical Co., Ltd.) are more preferred.
  • An ethylenically unsaturated compound having an acid group is also suitable, and examples of the commercially available product thereof include TO-756 which is a carboxyl group-containing Afunctional aery late and TO- 1382 which is a carboxyl group-containing pentafunctional acrylate, produced by Toagosei Co., Ltd.
  • examples of the highly heat resistant polymerizable compound include benzocyclobutene (BCB), bisallylnadiimide (BAND, benzoxazine, melamine and its analogues.
  • two or more kinds of the polymerizable compounds may be used.
  • the content of the polymerizable compound is preferably from 3 to 80% by weight, more preferably from 5 to 50% by weight, based on the total solid content of the infrared ray shielding composition according to the invention.
  • the polymerizable compound may be the same as or different from a binder (preferably, an alkali-soluble binder).
  • the polymerizable compound when the polymerizable compound is a polymer, the polymerizable compound may be the same as the alkali-soluble binder described in detail hereinafter (that is, the polymerizable compound may be the same component as the alkali-soluble binder).
  • the content of the polymerizable compound is preferably from 3 to 80% by weight, more preferably from 5 to 60% by weight, based on the total solid content of the infrared ray shielding composition according to the invention.
  • the infrared ray shielding composition according to the invention contains a fine particle of tungsten oxide containing an alkali metal.
  • the fine particle of tungsten oxide containing an alkali metal is an infrared ray blocking agent having high absorption for infrared ray (light having a wavelength approximately from 800 to 1,200 nm) (that is, the light shielding property (light blocking property) for infrared ray is high) and low absorption for visible light.
  • the infrared ray shielding composition according to the invention can form an infrared ray shielding film having a high light shielding property in the infrared region and high light transparency in the visible region by containing the fine particle of tungsten oxide containing an alkali metal.
  • the fine particle of tungsten oxide containing an alkali metal exhibits also small absorption for light shorter than the visible region, which is employed in exposure with a high-pressure mercury lamp, KrF, ArF or the like used in the image formation. Therefore, the excellent pattern is obtained by further incorporating an alkali-soluble binder into the infrared ray shielding composition containing the fine particle of tungsten oxide containing an alkali metal according to the invention.
  • the fine particle of tungsten oxide containing an alkali metal is preferably represented by formula (composition formula) (I) shown below.
  • M represents an alkali metal
  • W represents tungsten
  • O represents oxygen
  • the alkali metal represented by M may be one kind or two or more kinds.
  • the alkali metal represented by M is preferably Rb or Cs, and more preferably Cs.
  • z y is 2.2 or more, a chemical stability as the material can be more improved, and when it is 3.0 or less, an infrared ray can be sufficiently blocked.
  • the fine particle of tungsten oxide containing an alkali metal represented by formula (I) include Cs 033 WO 3 , Rb 0 . 33 WO 3 and Ko. 33 W0 3 .
  • the fine particle of tungsten oxide containing an alkali metal is preferably CS 033 WO 3 or Rb 033 WO 3 , and more preferably CS 033 WO 3 .
  • the average particle size of the fine particle of tungsten oxide containing an alkali metal is preferably 800 nm or less, more preferably 400 nm or less, and still more preferably 200 nm or less.
  • the average particle size is in the range described above, the fine particle of tungsten oxide containing an alkali metal can hardly block visible light by light scattering so that light transparency in the visible light region can be more ensured.
  • the average particle size is preferably smaller, but for reasons of easy handling property or the like at the production, the average particle size of the fine particle of tungsten oxide containing an alkali metal is preferably 1 run or more.
  • the content of the fine particle of tungsten oxide containing an alkali metal is preferably from 3 to 20% by weight, more preferably from 5 to 10% by weight, based on the total solid content of the infrared ray shielding composition according to the invention.
  • two or more kinds of the fine particles of tungsten oxide containing an alkali metal may be used.
  • the fine particle of tungsten oxide containing an alkali metal is available as a commercial product, and it can be obtained by a method of heat-treating a tungsten compound containing an alkali metal in an inert gas atmosphere or a reducing gas atmosphere (see, Japanese Patent No. 4,096,205).
  • a dispersion of the fine particle of tungsten oxide containing an alkali metal for example, YMF-02 produced by Sumitomo Metal Mining Co., Ltd. is available.
  • the infrared ray shielding composition according to the invention may contain a binder.
  • the binder can be appropriately selected according to the purpose, and examples thereof include a (meth)acrylic resin, a urethane resin, a polyvinyl alcohol, a polyvinyl butyral, a polyvinyl formal, a polyamide and a polyester, and preferably includes a (meth)acrylic resin and a urethane resin.
  • examples of the binder having no alkali solubility include a (meth)acrylic resin, a urethane resin, a polyvinyl alcohol, a polyvinyl butyral, a polyvinyl formal, a polyamide and a polyester each having no alkali solubility because of having no acid group and include a polymer obtained by polymerization of a polymerizable compound having no acid group described below.
  • the binder is preferably an alkali-soluble binder (alkali-soluble resin).
  • alkali-soluble binder alkali-soluble resin
  • the alkali-soluble binder is not particularly restricted as long as it is soluble in alkali, and can be appropriately selected according to the purpose.
  • examples thereof include a (meth)acrylic resin, a urethane resin, a polyvinyl alcohol, a polyvinyl butyral, a polyvinyl formal, a polyamide and a polyester, and preferably includes a (meth)acrylic resin and a urethane resin.
  • the alkali-soluble binder preferably has an acid group.
  • the acid group includes, for example, a carboxylic acid group, a sulfonic acid group, a phosphonic acid group, a phosphoric acid group and a sulfonamido group, and is preferably a carboxylic acid group from the standpoint of availability of raw materials.
  • the alkali-soluble binder having an acid group is not particularly restricted and is preferably a polymer obtained by using an acid group-containing polymerizable compound as a monomer component, and from the standpoint of adjustment of acid value, more preferably a copolymer obtained by copolymerizing a polymerizable compound having an acid group and a polymerizable compound having no acid group.
  • the polymerizable compound having an acid group is not particularly restricted and may be appropriately selected according to the purpose, and examples thereof include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid and p-carboxylstyrene. Among them, acrylic acid, methacrylic acid or p-carboxylstyrene is preferred.
  • the polymerizable compounds having an acid group may be used individually or in combination of two or more thereof.
  • the polymerizable compound having no acid group is not particularly restricted and suitable examples thereof include a (meth)acrylic acid ester (for example, an alkyl ester, an aryl ester or an aralkyl ester).
  • a (meth)acrylic acid ester for example, an alkyl ester, an aryl ester or an aralkyl ester.
  • the alkyl group in the alkyl ester moiety of the (meth)acrylic acid ester may be straight-chain or branched and is preferably an alkyl group having from 1 to 10 carbon atoms, and more preferably an alkyl group having from 1 to 6 carbon atoms.
  • the aryl group in the aryl ester moiety of the (meth)acrylic acid ester is preferably an aryl group having from 6 to 14 carbon atoms, and more preferably an aryl group having from 6 to 10 carbon atoms.
  • the aralkyl group in the aralkyl ester moiety of the (meth)acrylic acid ester is preferably an aralkyl group having from 7 to 20 carbon atoms, and more preferably an aralkyl group having from 7 to 12 carbon atoms.
  • the molar ratio between the monomer corresponding to the polymerizable compound having an acid group and the monomer corresponding to the polymerizable compound having no acid group is ordinarily from 1 : 99 to 99 : 1, preferably from 30 : 70 to 99 : 1, and more preferably
  • the content of the acid group in the alkali-soluble binder is not particularly restricted and is preferably from 0.5 to 4.0 meq/g, and more preferably from 0.5 to 3.0 meq/g.
  • the content of the acid group is 0.5 meq/g or more, the alkali development property is sufficiently obtained and an excellent pattern can be more steadily obtained.
  • the content of the acid group is 4.0 meq/g or less, the risk of impairing the strength of the infrared ray shielding film in which the pattern is formed can be surely avoided.
  • the alkali-soluble binder preferably further has a crosslinkable group and by the introduction of crosslinkable group, both curing property of the exposed area and alkali development property of the unexposed area can be particularly improved.
  • the introduction of crosslinkable group is also preferred because a pattern having high durability is obtained (in particular, this effect is significant when higher durability is required of the solder resist, for example, in the case where the wiring density of metal wiring covered with the solder resist is high).
  • the crosslinkable group is a group capable of crosslinking the binder polymer in the course of a polymerization reaction occurring in the photosensitive layer when the photosensitive layer obtained from the infrared ray shielding composition (polymerizable composition) is exposed or heated.
  • the crosslinkable group is not particularly restricted as long as it is a group having such a function, and examples thereof include as a functional group capable of undergoing an addition polymerization reaction, an ethylenically unsaturated bond group, an amino group and an epoxy group.
  • the crosslinking group may also be a functional group capable of forming a radical upon irradiation with light, and examples thereof include a thiol group and a halogen group. Among them, an ethylenically unsaturated bond group is preferred.
  • the ethylenically unsaturated bond group is preferably a styryl group, a (meth)acryloyl group or an allyl group and from the standpoint of satisfying both stability of the crosslinkable group before exposure and strength of the infrared ray shielding film in which the pattern is formed, more preferably a (meth)acryloyl group.
  • a free radical a polymerization initiating radical or a propagating radical in the course of polymerization of the polymerizable compound
  • a free radical a polymerization initiating radical or a propagating radical in the course of polymerization of the polymerizable compound
  • crosslinking is formed between the polymer molecules to effect curing.
  • an atom for example, a hydrogen atom on a carbon atom adjacent to the functional crosslinkable group
  • polymer radicals combine with each other to form crosslinking between the polymer molecules, whereby curing is effected.
  • the content of the crosslinkable group in the alkali-soluble binder is not particularly restricted and is preferably from 0.5 to 3.0 meq/g, more preferably from 1.0 to 3.0 meq/g, and particularly preferably from 1.5 to 2.8 meq/g.
  • the content (meq/g) can be measured, for example, by iodine number titration.
  • alkali-soluble binder having a crosslinkable group is described in detail in JP-A-2003-262958 and compounds described therein can also be used in the invention.
  • the alkali-soluble binder having a crosslinkable group is preferably an alkali-soluble binder having an acid group and a crosslinkable group and the representative examples thereof are described below.
  • a urethane-modified polymerizable double bond-containing acrylic resin obtained by a reaction of a compound in which an isocyanate group and a hydroxy group are previously reacted to leave one unreacted isocyanate group and which has at least one (meth)acryloyl group with an acrylic resin containing a carboxyl group.
  • An unsaturated group-containing acrylic resin obtained by reacting an acrylic resin containing a carboxyl group with a compound having both an epoxy group and a polymerizable double bond in its molecule.
  • a polymerizable double bond-containing acrylic resin obtained by reacting an acrylic resin containing a hydroxy group with a dibasic acid anhydride having a polymerizable double bond.
  • the resins of (1) and (2) are preferred.
  • examples of the alkali-soluble binder having an acid group and a crosslinkable group include a polymer compound having an acidic group and an ethylenically unsaturated bond in its side chain and having a bisphenol A-type skeleton or a bisphenol F-type skeleton and a novolac resin and resol resin each having an acidic group and an ethylenically unsaturated bond.
  • These resins can be obtained by a method described in paragraphs [0008] to [0027] of JP-A-11-240930.
  • the alkali-soluble binder is preferably a (meth)acrylic resin or a urethane resin.
  • the "(meth)acrylic resin” is preferably a copolymer having, as a polymerization component, a (meth)acrylic acid derivative, for example, (meth)acrylic acid, a (meth)acrylic acid ester (e.g., an alkyl ester, an aryl ester or an aralkyl ester), (meth)acrylamide and a (meth)acrylamide derivative.
  • the "urethane resin” is preferably a polymer produced by a condensation reaction between a compound having two or more isocyanate groups and a compound having two or more hydroxy groups.
  • Suitable examples of the (meth)acrylic resin include a copolymer containing a repeating unit having an acid group.
  • Suitable examples of the acid group include those described above.
  • the repeating unit having an acid group is preferably a repeating unit derived from (meth)acrylic acid or a repeating unit represented by formula (I) shown below.
  • R represents a hydrogen atom or a methyl group
  • R represents a single bond or an (n+l)-valent connecting group
  • A represents an oxygen atom or -NR 3 -
  • R 3 represents a hydrogen atom or a monovalent hydrocarbon group having from 1 to 10 carbon atoms
  • n represents an integer from 1 to 5.
  • the connecting group represented by R 2 is preferably composed of one or more kinds of atoms selected from the group consisting of a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom and a halogen atom, and the number of atoms constituting the connecting group represented by R 2 is preferably from 1 to 80.
  • Specific examples of the connecting group include an alkylene group and an arylene group, and the connecting group may have a structure where a plurality of these divalent groups are connected by any of an amido bond, an ether bond, a urethane bond, a urea bond and an ester bond.
  • R 2 is preferably a single bond, an alkylene group or a structure where a plurality of alkylene groups are connected by at least any of an amido bond, an ether bond, a urethane bond, a urea bond and ester bond.
  • the carbon number of the alkylene group is preferably from 1 to 5, and more preferably from 1 to 3.
  • the carbon number of the arylene group is preferably from 6 to 14, and more preferably from 6 to 10.
  • the alkylene group and arylene group may further have a substituent and the substituent includes a monovalent nonmetallic atomic group excluding a hydrogen atom.
  • substituents include a halogen atom (-F, -Br, -CI or -I), a hydroxy group, a cyano group, an alkoxy group, an aryloxy group, a mercapto group, an alkylthio group, an arylthio group, an alkylcarbonyl group, an arylcarbonyl group, a carboxyl group and its conjugate base group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an aryl group, an alkenyl group and an alkynyl group.
  • the hydrocarbon group represented by R 3 preferably has a carbon number from 1 to 10, more preferably from 1 to 5, and still more preferably from 1 to 3.
  • R is most preferably a hydrogen atom or a methyl group.
  • n is preferably 1 to 3, more preferably 1 or 2, and most preferably 1.
  • the ratio (% by mole) of the acid group-containing repeating unit based on the total repeating unit of the (meth)acrylic resin is preferably from 10 to 90% from the standpoint of development property. In consideration of satisfying both the development property and the strength of the infrared ray shielding film in which the pattern is formed, it is more preferably from 50 to 85%, and particularly preferably from 60 to 80%.
  • the (meth)acrylic resin preferably further has a crosslinkable group, and the specific examples and content of the crosslinkable group are the same as those described above.
  • the (meth)acrylic polymer for use in the invention may contain, in addition to the polymerization unit having an acid group and the polymerization unit having a crosslinkable group, a polymerization unit composed of an alkyl or aralkyl (meth)acrylate, a polymerization unit composed of (meth)acrylamide or its derivative, a polymerization unit composed of an a-hydroxymethyl acrylate or a polymerization unit composed of a styrene derivative.
  • the alkyl group in the alkyl (meth)acrylate is preferably an alkyl group having from 1 to 5 carbon atoms or an alkyl group containing the substituent described above and having from 2 to 8 carbon atoms, and more preferably a methyl group.
  • Examples of the aralkyl (meth)acrylate include benzyl (meth)acrylate.
  • Examples of the (meth)acrylamide derivative include N-isopropylacrylamide, N-phenylmethacrylamide, N-(4-methoxycarbonylphenyl)methacrylamide, N,N-dimethylacrylamide and mo holinoacrylamide.
  • Examples of the a-hydroxymethyl acrylate include ethyl a-hydroxymethyl acrylate and cyclohexyl ⁇ -hydroxymethyl acrylate.
  • Examples of the styrene derivative include styrene and 4-tert-butylstyrene.
  • the "urethane resin” is preferably a urethane resin having, as the basic skeleton, a structural unit represented by a reaction product between at least one diisocyanate compound represented by formula (1) shown below and at least one diol compound represented by formula (2) shown below.
  • X and L 1 each independently represent a divalent organic residue.
  • At least one diol compound represented by formula (2) preferably has an acid group.
  • an alkali-soluble urethane resin having the acid group introduced can be suitably produced as a reaction product of the diisocyanate compound and the diol compound.
  • an alkali-soluble urethane resin can be more easily produced than in the case of substituting and introducing an acid group in the desired side chain after the reaction and production of a urethane resin.
  • At least one compound of the diisocyanate compound represented by formula (1) and the diol compound represented by formula (2) preferably has a crosslinkable group.
  • the crosslinkable group include those described above.
  • an alkali-soluble urethane resin having the crosslinkable group introduced can be suitably produced as a reaction product of the diisocyanate compound and the diol compound.
  • a crosslinkable group-containing urethane resin can be more easily produced than in the case of substituting and introducing a crosslinkable group in the desired side chain after the reaction and production of a urethane resin.
  • X is preferably a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group or a group formed by combination thereof, and a number of carbon atoms included is preferably from 1 to 20, and more preferably from 1 to 15.
  • the divalent aliphatic or aromatic hydrocarbon group may further has a substituent incapable of reacting with an isocyanate group.
  • diisocyanate compound represented by formula (1) examples include an aromatic diisocyanate compound, for example, 2,4-tolylene diisocyanate, 2,4-tolylene diisocyanate dimer, 2,6-tolylene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate,
  • 3,3 '-dimethylbiphenyl-4,4' -diisocyanate an aliphatic diisocyanate compound, for example, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate or dimer acid diisocyanate; an alicyclic diisocyanate compound, for example, isophorone diisocyanate, 4,4'-methylenebis(cyclohexylisocyanate), methylcyclohexane-2,4 (or 2,6)-diisocyanate or l,3-(isocyanatomethyl)cyclohexane; and a diisocyanate compound which is a reaction product of a diol with a diisocyanate, for example, adduct of 1 mole of 1,3-butylene glycol and 2 moles of tolylene diisocyanate.
  • a diisocyanate compound which is a reaction product of a dio
  • examples of such a diisocyanate compound include a product obtained by addition-reacting a triisocyanate compound with one equivalent of a monofunctional alcohol or monofunctional amine compound having a crosslinkable group (for example, an ethylenically unsaturated bond group).
  • a triisocyanate compound and the monofunctional alcohol or monofunctional amine compound having a crosslinkable group include those described in paragraphs [0034], [0035] and [0037] to [0040] of Japanese Patent No. 4,401,262, but the invention should not be construed as being limited thereto.
  • diisocyanate compound having a crosslinkable group examples include those described in paragraphs [0042] to [0049] of Japanese Patent No. 4,401,262, but the invention should not be construed as being limited thereto.
  • Examples of the diol compound represented by formula (2) widely include a polyether diol compound, a polyester diol compound and a polycarbonate diol compound.
  • the polyether diol compound includes compounds represented by formulae (3), (4), (5), (6) and (7) shown below, and a random copolymer of ethylene oxide and propylene oxide having a hydroxy group at the terminal.
  • R 14 represents a hydrogen atom or a methyl group
  • X 1 represents a group shown below
  • a, b, c, d, e, f and g each represents an integer of 2 or more and is preferably an integer from 2 to 100.
  • Two ds may be the same or different.
  • two X's may be the same or different.
  • polyether diol compound represented by formulae (3) and (4) include diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, heptaethylene glycol, octaethylene glycol, di-l,2-propylene glycol, tri-l,2-propylene glycol, tetra- 1,2-propylene glycol, hexa-l,2-propylene glycol, di- 1,3 -propylene glycol, tri- 1,3 -propylene glycol, tetra- 1,3 -propylene glycol, di-l,3-butylene glycol, tri-l,3-butylene glycol, hexa-l,3-butylene glycol, polyethylene glycol having weight average molecular weight of 1,000, polyethylene glycol having weight average molecular weight of 1,500, polyethylene glycol having weight average molecular weight of 2,000, polyethylene glycol having weight average molecular weight of 3,000,
  • polyether diol compound represented by formula (5) examples include PTMG650, PTMG1000, PTMG2000 and PTMG3000 (produced by Sanyo Chemical Industries, Ltd.).
  • polyether diol compound represented by formula (6) examples include NEWPOL PE-61, NEWPOL PE-62, NEWPOL PE-64, NEWPOL PE-68, NEWPOL PE-71, NEWPOL PE-74, NEWPOL PE-75, NEWPOL PE-78, NEWPOL PE-108, NEWPOL PE-128 and NEWPOL PE-61 (produced by Sanyo Chemical Ind., Ltd.).
  • polyether diol compound represented by formula (7) examples include NEWPOL BPE-20, NEWPOL BPE-20F, NEWPOL BPE-20NK, NEWPOL BPE-20T, NEWPOL BPE-20G, NEWPOL BPE-40, NEWPOL BPE-60, NEWPOL BPE-100, NEWPOL BPE-180, NEWPOL BPE-2P, NEWPOL BPE-23P, NEWPOL BPE-3P and NEWPOL BPE-5P (produced by Sanyo Chemical Ind., Ltd.).
  • Random copolymer of ethylene oxide and propylene oxide having a hydroxy group at the terminal include NEWPOL 50HB-100, NEWPOL 50HB-260, NEWPOL 50HB-400, NEWPOL 50HB-660, NEWPOL 50HB-2000 and NEWPOL 50HB-5100 (produced by Sanyo Chemical Ind., Ltd.).
  • the polyester diol compound includes compounds represented by formulae (8) and (9) shown below.
  • L 2 , L 3 and L 4 each represents a divalent aliphatic or aromatic hydrocarbon group
  • L 5 represents a divalent aliphatic hydrocarbon group.
  • L 2 , L 3 and L 5 may be the same as or different from each other.
  • each of L 2 to L 4 represents an alkylene group, an alkenylene group, an alkynylene group or an arylene group
  • L 5 preferably represents an
  • nl and n2 each represents an integer of 2 or more, and preferably an integer from 2 to 100.
  • the polycarbonate diol compound includes a compound represented by formula (10) shown below. o
  • L 6 s which may be the same or different, each represents a divalent aliphatic or aromatic hydrocarbon group.
  • L 6 preferably represents an alkylene group, an alkenylene group, an alkynylene group or an arylene group.
  • other bond or functional group incapable of reacting with an isocyanate group for example, an ether bond, a carbonyl bond, an ester bond, a cyano group, an olefin bond, a urethane bond, an amido group, a ureido group or a halogen atom may be present.
  • n3 represents an integer of 2 or more, preferably an integer from 2 to 100.
  • diol compounds represented by formulae (8), (9) and (10) include Compound Nos. 1 to 18 set forth below.
  • n represents an integer of 2 or more.
  • a diol compound having a substituent incapable of reacting with an isocyanate group may also be used in combination.
  • a diol compound includes, for example, compounds represented by formulae (11) and (12) shown below.
  • L and L which may be the same or different, each represents a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group or a divalent
  • L and L other bond or functional group incapable of reacting with an isocyanate group, for example, a carbonyl bond, an ester bond, a urethane bond, an amido group or a ureido group may be present, if desired.
  • L 7 and L 8 may be combined with each other to form a ring.
  • the divalent aliphatic hydrocarbon group, aromatic hydrocarbon group and heterocyclic group may have a substituent, and examples of the substituent include an alkyl group, an aralkyl group, an aryl group, an alkoxy group, an aryloxy group and a halogen atom, for example, -F, -CI, -Br or -I.
  • At least one of the diol compounds is preferably a diol compound having an acid group, as the diol compound having a substituent incapable of reacting with an isocyanate group described above.
  • Specific examples of the acid group include those described above and the acid group is preferably a carboxylic acid group.
  • the diol compound having a carboxylic acid group includes, for example, compounds represented by formulae (13) to (15) shown below.
  • R 15 represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, an alkoxy group or an aryloxy group, preferably a hydrogen atom, an alkyl group having from 1 to 8 carbon atoms or an aryl group having from 6 to 15 carbon atoms.
  • the alkyl group, aralkyl group, aryl group, alkoxy group and aryloxy group may have a substituent and examples of the substituent include a cyano group, a nitro group, a halogen atom, for' example, -F, -CI, -Br or -I, -CONH 2 , -COOR 16 , -OR 16 , -NHCONHR 16 , -NHCOOR 16 , -NHCOR 16 and -OCONHR 16 (wherein R 16 represents an alkyl group having from 1 to 10 carbon atoms or an aralkyl group having from 7 to 15 carbon atoms).
  • L 9 , L 10 and L 11 which may be the same or different, each represents a single bond or a divalent aliphatic or aromatic hydrocarbon group, preferably an alkylene group having from 1 to 20 carbon atoms or an arylene group having from 6 to 15 carbon atoms, and more preferably an alkylene group having from 1 to 8 carbon atoms.
  • the divalent aliphatic or aromatic hydrocarbon group may have a substituent and examples of the substituent include an alkyl group, an aralkyl group, an aryl group, an alkoxy group and a halogen atom.
  • L 9 to L 11 may have other functional group incapable of reacting with an isocyanate group, for example, a group containing a carbonyl, ester, urethane, amido, ureido or ether group.
  • R 15 , L 7 , L 8 and L 9 may be combined with each other to form a ring.
  • Ar represents a trivalent aromatic hydrocarbon group which may have a substituent, and preferably represents an aromatic group having from 6 to 15 carbon atoms.
  • diol compound having a carboxyl group represented by formulae (13) to (15) include 3,5-dihydroxybenzoic acid, 2,2-bis(hydroxymethyl)propionic acid, 2,2-bis(2-hydroxyethyl)propionic acid, 2,2-bis(3-hydroxypropyl)propionic acid, bis(hydroxymethyl)acetic acid, bis(4-hydroxyphenyl)acetic acid, 2,2-bis(hydroxymethyl)butyric acid, 4,4-bis(4-hydroxyphenyl)pentanoic acid, tartaric acid, N,N-dihydroxyethylglycine, and N,N-bis(2-hydroxyethyl)-3 -carboxypropionamide.
  • a method using a diol compound having an unsaturated group as a raw material for the production of polyurethane resin is also suitable.
  • a diol compound may be a commercially available product, for example, trimethylolpropane monoallyl ether or may be a compound easily produced by a reaction of a halogenated diol compound, a triol compound or an aminodiol compound with a carboxylic acid, acid chloride, isocyanate, alcohol, amine, thiol or alkyl halide compound having an unsaturated group.
  • Specific examples of the diol compound having a crosslinkable group include compounds described in paragraphs [0057] to [0066] of Japanese Patent No. 4,401,262, but the invention should not be construed as being limited thereto.
  • Compound Nos. 13 to 17 set forth above correspond to the diol compound represented by formula (8), (9) or (10) and are also the diol compound having a crosslinkable group.
  • a compound obtained by ring-opening of tetracarboxylic acid dianhydiide represented by any one of formulae (16) to (18) shown below with a diol compound may also be used in combination.
  • L represents a single bond, a divalent aliphatic or aromatic hydrocarbon group which may have a substituent (preferably, for example, an alkyl group, an aralkyl group, an aryl group, an alkoxy group, a halogeno group, an ester group or an amido group), -CO-, -SO-, -S0 2 -, -O- or -S-, and preferably represents a single bond, a divalent aliphatic hydrocarbon group having from 1 to 15 carbon atoms, -CO-, -S0 2 -, -O- or -S-.
  • a substituent preferably, for example, an alkyl group, an aralkyl group, an aryl group, an alkoxy group, a halogeno group, an ester group or an amido group
  • -CO- preferably, for example, an alkyl group, an aralkyl group, an aryl group, an alkoxy group, a
  • the divalent aliphatic or aromatic hydrocarbon group may have a substituent, and examples of the substituent include an alkyl group, an aralkyl group, an aryl group, an alkoxy group, a halogen . atom, an ester bond-containing group (for example, an alkylcarbonyloxy group, an alkyloxycarbonyl group, an arylcarbonyloxy group or an aryloxycarbonyl group) and an amido group.
  • substituent include an alkyl group, an aralkyl group, an aryl group, an alkoxy group, a halogen . atom, an ester bond-containing group (for example, an alkylcarbonyloxy group, an alkyloxycarbonyl group, an arylcarbonyloxy group or an aryloxycarbonyl group) and an amido group.
  • R" and R which may be the same or different, each represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, an alkoxy group or a halogeno group, preferably a hydrogen atom, an alkyl group having from 1 to 8 carbon atoms, an aryl group having from 6 to 15 carbon atoms, an alkoxy group having from 1 to 8 carbon atoms or a halogeno group.
  • Two ofL 12 , R 17 and R 18 may be combined with each other to form a ring.
  • R 19 and R 20 which may be the same or different, each represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group or a halogeno group, preferably a hydrogen atom, an alkyl group having from 1 to 8 carbon atoms or an aryl group having from 6 to 15 carbon atoms.
  • Two of L , R' and R u may be combined with each other to form a ring.
  • L 13 and L 14 which may be the same or different, each represents a single bond, a double bond or a divalent aliphatic hydrocarbon group, preferably a single bond, a double bond or a methylene group.
  • A represents a mononuclear or multinuclear aromatic ring, preferably an aromatic ring having from 6 to 18 carbon atoms.
  • 3,3',4,4'-benzophenonetetracarboxylic dianhydride 3,3',4,4'-diphenyltetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 4,4'-sulfonyldiphthalic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride,
  • Examples of the method for introducing a compound obtained by ring-opening of the tetracarboxylic dianhydride with a diol compound into a polyurethane resin include: a) a method of reacting a diisocyanate compound with an alcohol-terminated compound obtained by ring-opening of the tetracarboxylic dianhydride with a diol compound, and b) a method of reacting the tetracarboxylic dianhydride with an alcohol-terminated urethane compound obtained by reacting a diisocyanate compound under diol compound-excess conditions.
  • diol compound used for the ring-opening reaction examples include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, neopentyl glycol, 1,3-butylene glycol, 1,6-hexanediol, 2-butene-l,4-diol, 2,2,4-trirnethyl-l ,3-pentanediol,
  • the urethane resin described above is synthesized by adding the diisocyanate compound and the diol compound together with a known catalyst having an activity according to the reactivities of respective compounds in an aprotic solvent and heating the solution.
  • the molar ratio (M a : M b ) between the diisocyanate compound and the diol compound used for the synthesis is preferably from 1 : 1 to 1.2 : 1. It is preferred that a product having the desired physical property, for example, molecular weight or viscosity is finally synthesized in the form of containing no residual isocyanate group by undergoing treatment with an alcohol, amine or the like.
  • a urethane resin having a crosslinkable group (for example, an unsaturated group) in the terminal or main chain of the polymer is also suitably used.
  • a crosslinkable group for example, an unsaturated group
  • the crosslinking reactivity between the polymerizable compound and the urethane resin or between the urethane resins is enhanced so that the strength of the infrared ray shielding film in which the pattern is formed is increased.
  • the unsaturated group has a carbon-carbon double bond because of easy occurrence of the crosslinking reaction.
  • the method for introducing a crosslinkable group into the polymer terminal includes the following method. Specifically, the introduction may be attained by using an alcohol, amine or the like having a crosslinkable group in the step of treating the residual isocyanate group in the polymer terminal with an alcohol, amine or the like in the process for the synthesis of urethane resin described above. Specific examples of the compound include the compounds described above as the monofunctional alcohol or monofunctional amine compound having a crosslinkable group.
  • the crosslinkable group is more preferably introduced into the polymer side chain than into the polymer terminal from the standpoint in that the introduction amount is easily controlled, in that the introduction amount can be increased and in that the crosslinking reaction efficiency is enhanced.
  • the method for introducing a crosslinkable group into the main chain includes a method where a diol compound having an unsaturated group in the main chain direction is used for the synthesis of the urethane resin.
  • a diol compound having an unsaturated group in the main chain direction include cis-2-butene-l,4-diol, trans-2-butene-l,4-diol and polybutadiene diol.
  • alkali-soluble binder other than the (meth)acrylic resin and urethane resin acetal-modified polyvinyl alcohol binder polymers having an acid group described, for example, in European Patents 993,966 and 1,204,000 and JP-A-2001-318463 are suitable because of excellence balance between the film strength and development property.
  • polyvinylpyrrolidone, polyethylene oxide or the like is useful as a water-soluble linear organic polymer.
  • alcohol-soluble nylon a polyether of 2,2-bis(4-hydroxyphenyl)propane and epichlorohydrin or the like is also useful.
  • a [benzyl (meth)acrylate/(meth)acrylic acid/and, if desired, other addition-polymerizable vinyl monomer] copolymer or an [allyl (meth)acrylate/(meth)acrylic acid/and, if desired, other addition-polymerizable vinyl monomer] copolymer is suitable because of excellent balance of the film strength, sensitivity and development property.
  • the weight average molecular weight of the binder polymer which can be used in the infrared ray shielding composition according to the invention is preferably 3,000 or more, more preferably in a range from 5,000 to 300,000, and most preferably in a range from 10,000 to 30,000, and the number average molecular weight thereof is preferably 1,000 or more, and more preferably in a range from 2,000 to 250,000.
  • the polydispersity is preferably 1 or more, and more preferably in a range from 1.1 to 10.
  • the alkali-soluble binder may be any of a random polymer, a block polymer, a graft polymer or the like.
  • the binder (preferably alkali-soluble binder) can be synthesized by a conventionally known method.
  • the solvent used at the synthesis include tetrahydrofuran, ethylene dichloride, cyclohexanone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate and butyl acetate.
  • the solvents may be used individually or as a mixture of two or more thereof.
  • the binders may be used individually or in combination of two or more thereof.
  • the content of the binder is preferably from 5 to 80% by weight, more preferably from 30 to 60% by weight, based on the total solid content of the infrared ray shielding composition according to the invention.
  • the content of the binder is in the range described above, the exposure sensitivity is good, the processing is conducted for only a short time, and good thermal cycle test resistance (TCT resistance) is obtained.
  • the infrared ray shielding composition according to the invention may contain an infrared ray blocking agent (hereinafter, also referred to as "other infrared ray blocking agent”) other than the fine particle of tungsten oxide containing an alkali metal within the range not impairing the effects of the invention.
  • the other infrared ray blocking agent is preferably a compound having absorption in a wavelength range from 800 to 1,200 nm and exhibiting good transparency to light used for exposure. From such a standpoint, the other infrared ray blocking agent is preferably selected from an infrared absorbing dye and an infrared absorbing inorganic pigment.
  • the infrared absorbing dye examples include a cyanine dye, a phthalocyanine dye, a naphthalocyanine dye, an immonium dye, an aminium dye, a quinolium dye, a pyrylium dye and a metal complex dye, for example, aNi complex dye.
  • the dye usable as the infrared ray blocking agent is also available as a commercial product, and suitable examples thereof include the following commercially available dyes:
  • YKR-4010 YKR-3030, YK -3070, MIR-327, MIR-371, SIR-159, PA-1005, MIR-369, MIR-379, SIR-128, PA-1006, YKR-2080, MIR-370, YKR-3040, YKR-3081, SIR-130, MIR-362, YKR-3080, SIR-132 and PA-1001, produced by Yamamoto Chemicals Inc.;
  • a phmalocyanine dye and a metal complex dye are preferred from the standpoint of heat resistance.
  • the dyes may be used individually, or for the purpose of exhibiting a good light shielding property in a wavelength range from 800 to 1,200 nm, two or more of the dyes may be used in combination according to the purpose.
  • Examples of the infrared absorbing inorganic pigment usable as the other infrared ray blocking agent include zinc flower, lead white, lithopone, titanium oxide, chromium oxide, iron oxide, sedimentating barium sulfate, barite powder, red lead, iron oxide red, lead yellow, zinc yellow (zinc yellow class 1, zinc yellow class 2), ultramarine blue, Prussia blue (iron/potassium ferrocyanide), zircon grey, praseodymium yellow, chrome-titanium yellow, chrome green, peacock, Victoria green, iron blue (irrelevant to Prussia blue), vanadium-zirconium blue, chrome-tin pink, manganese pink and salmon pink.
  • black pigment examples include a metal oxide, a metal nitride or a mixture thereof, containing one or two or more metal elements selected from the group consisting of Co, Cr, Cu, Mn, Ru, Fe, Ni, Sn, Ti and Ag.
  • the black pigment is preferably titanium black which is a black pigment containing titanium nitride because of its good blocking property in the infrared region of a wavelength from 800 to 1,200 nm.
  • the titanium black can be obtained by a known method. Also, as a commercially available product, titanium black produced, for example, by Ishihara Sangyo Kaisha, Ltd., Ako Kasei Co., Ltd., JEMCO Inc., Mitsubishi Materials Corp. or Mitsubishi Materials Electronic Chemicals Co., Ltd. may be used.
  • the titanium black indicates a black particle containing titanium atom. It is preferably low-order titanium oxide, titanium oxynitride or the like.
  • As the titanium black particle a particle whose surface is modified for the purposes, for example, of enhancing the dispersibility or inhibiting aggregation may be used, if desired.
  • the surface modification method includes a method of covering the surface with one or more oxides selected from silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide and zirconium oxide. Also, the surface may be treated with a water-repellent substance as described in paragraphs [0010] to [0027] of JP-A-2007-302836.
  • Examples of the method for producing titanium black include a method of heating and reducing a mixture of titanium dioxide and metal titanium in a reductive atmosphere (see, JP-A-49-5432), a method of reducing ultrafine titanium dioxide obtained by high-temperature hydrolysis of titanium tetrachloride, in a reductive atmosphere containing hydrogen (see, JP-A-57-205322), a method of reducing titanium dioxide or titanium hydroxide at high temperature in the presence of ammonia (see, JP-A-60-65069 and JP-A-61-201610), and a method of attaching a vanadium compound to titanium dioxide or titanium hydroxide and then reducing it at high temperature in the presence of ammonia (see, JP-A-61-201610), but the method should not be construed as being limited thereto.
  • the particle size of the titanium black particle is not particularly restricted and is preferably from 3 to 2,000 nm, more preferably from 10 to 500 nm, from the standpoint of dispersibility and colorability.
  • the specific surface area of titanium black is not particularly restricted and a value measured by a BET method is ordinarily approximately from 5 to 150 m /g, preferably approximately from 20 to 100 m /g, in order to obtain a predetermined water-repellent property after the surface treatment of titanium black with a water repelling agent.
  • the particle size of the inorganic pigment used as the other infrared ray blocking agent is, in terms of the average particle size, preferably from 3 nm to 0.01 mm, and from the standpoint of dispersibility, light-shielding property and sedimentation property with lapse of time, the average particle size is preferably from 10 nm to 1 ⁇ .
  • the infrared ray shielding composition according to the invention may or may not contain the other infrared ray blocking agent, and in the case of containing the other infrared ray blocking agent, the content thereof is preferably from 5 to 75% by weight, more preferably from 10 to 40% by weight, based on the weight of the fine particle of tungsten oxide containing an alkali metal.
  • the fine particle of tungsten oxide containing an alkali metal may be dispersed to use employing a known dispersing agent for the purpose of enhancing dispersibility and dispersion stability of the fine particle of tungsten oxide in the infrared ray shielding composition.
  • the dispersing agent which can be used in the invention includes a polymer dispersing agent (for example, polyamidoamine and salt thereof, polycarboxylic acid and salt thereof, a high molecular weight unsaturated acid ester, a modified polyurethane, a modified polyester, a modified poly(meth)acrylate, a (meth)acrylic copolymer or a naphthalenesulfonic acid-formalin condensate), and a surfactant, for example, a polyoxyethylene alkyl phosphate ester, a polyoxyethylene alkylamine or an alkanolamine.
  • a polymer dispersing agent for example, polyamidoamine and salt thereof, polycarboxylic acid and salt thereof, a high molecular weight unsaturated acid ester, a modified polyurethane, a modified polyester, a modified poly(meth)acrylate, a (meth)acrylic copolymer or a naphthalenesulfonic acid
  • the polymer dispersing agent can be further classified into a straight-chain polymer, a terminal-modified polymer, a graft polymer and a block polymer according to its structure.
  • terminal-modified polymer having an anchor moiety to the surface examples include polymers having a phosphoric acid group at the terminal described in JP-A-3- 112992 and JP-T-2003-533455 (the term "JP-T” as used herein means a published Japanese translation of a PCT patent application), polymers having a sulfonic acid group at the terminal described in JP-A-2002-273191, polymers having an organic dye partial structure or a heterocyclic ring described in JP-A-9-77994 and polymers produced by modifying an oligomer or polymer having a hydroxy group or an amino group at one terminal with an acid anhydride described in JP-A-2008-29901.
  • a polymer in which two or more anchor moieties (for example, an acid group, a basic group, an organic dye partial structure or a heterocyclic ring) to the surface of infrared ray blocking agent are introduced into the polymer terminal described in JP-A-2007-277514 is also preferred because of its excellent dispersion stability.
  • Examples of the graft polymer having an anchor moiety to the surface include reaction products of a poly(lower alkylene imine) and a polyester described in JP-A-54-37082, JP-T-8-507960 and JP-A-2009-258668, reaction products of a polyallylamine and a polyester described in JP-A-9- 169821, amphoteric dispersing resins having a basic group and an acidic group described in JP-A-2009-203462, copolymers of a macromonomer and a nitrogen atom-containing monomer described in JP-A-10-339949 and JP-A-2004-37986, graft polymers having an organic dye partial structure or a heterocyclic ring described in JP-A-2003-238837, JP-A-2008-9426 and JP-A-2008-81732 and copolymers of a macromonomer and an acid group-containing monomer described in JP-A-2010-106268.
  • a known macromonomer may be used and examples thereof include MACROMONOMER AA-6 (a polymethyl methacrylate having a terminal group of a methacryloyl group), AS-6 (a polystyrene having a terminal group of a methacryloyl group), AN-6S (a copolymer of an acrylonitrile and a styrene having a terminal group of a methacryloyl group) and AB-6 (a polybutyl acrylate having a terminal group of a methacryloyl group) produced by Toagosei Co., Ltd.; PLACCEL FM5 (a 5 molar equivalent adduct of ⁇ -caprolactone to 2-hydroxyethyl methacrylate) and FA10L (a 10 molar equivalent adduct of ⁇ -caprolactone to 2-hydroxyethyl
  • a polyester macromonomer excellent in flexibility and solvent affinity is preferred from the standpoint of dispersibility and dispersion stability of the infrared ray blocking agent in the infrared ray shielding composition, and a polyester macromonomer represented by the polyester macromonomer described in JP-A-2-272009 is most preferred.
  • block polymers having an anchor moiety to the surface block polymers described, for example, in JP-A-2003-491 10 and JP-A-2009-52010 are preferred.
  • the dispersing agent which can be used may be appropriately selected, for example, from known dispersing agents and surfactants.
  • Disperbyk-101 polyarnidoarnine phosphate
  • 107 carboxylic acid ester
  • 110 copolymer containing an acid group
  • 130 polyamide
  • 161, 162, 163, 164, 165, 166, 170 high molecular weight copolymer
  • BYK-P104 PI 05 (high molecular weight unsaturated polycarboxylic acid) produced by Byk-Chemie
  • EFKA 4047, 4050-4010-4165 polyurethane-based
  • EFKA 4330-4340 block copolymer
  • 4400-4402 modified polyacrylate
  • 5010 polyyester amide
  • 5765 high molecular weight polycarboxylate
  • 6220 fatty acid polyester
  • 6745 phthalocyanine derivative
  • the dispersing agents may be used individually or in combination of two or more thereof.
  • the terminal-modified polymer, graft polymer or block polymer having an anchor moiety to the surface of the infrared ray blocking agent may be also used in combination with an alkali-soluble resin.
  • alkali-soluble resin examples include a (meth)acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, a partially esterified maleic acid copolymer, an acidic cellulose derivative having a carboxylic acid in its side chain and a resin obtained by modifying a hydroxy group-containing polymer with an acid anhydride, and particularly a (meth)acrylic acid copolymer is preferred.
  • a (meth)acrylic acid copolymer examples include a (meth)acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, a partially esterified maleic acid copolymer, an acidic cellulose derivative having a carboxylic acid in its side chain and a resin obtained by modifying a hydroxy group-containing polymer with an acid anhydride, and particularly a (meth
  • N-position substituted maleimide monomer copolymers described in JP-A- 10-300922, ether dimer copolymers described in JP-A-2004-300204 and polymerizable group-containing alkali-soluble resins described in JP-A-7-319161 are preferred.
  • resins described in JP-A-2010-106268 shown below are preferred.
  • a polymer dispersing agent having a polyester chain in its side chain is preferred, and a resin having an acid group and a polyester chain is also suitable.
  • the acid group in the dispersing agent in view of adsorptivity, an acid group having a pKa of 6 or less is preferred, and a carboxylic acid, a sulfonic acid or a phosphoric acid is more preferred.
  • the dispersing agent is preferably a graft copolymer having a graft chain selected from a polyester structure, a polyether structure and a polyacrylate structure, in which the number of atoms excluding hydrogen atoms is from 40 to 10,000, and the graft copolymer preferably contains at least a structural unit represented by any of formulae (1) to (4) shown below, more preferably contains at least a structural unit represented by any of formulae (1 A), (2A), (3A), (3B) and (4) shown below.
  • atom or a monovalent organic group is preferably a hydrogen atom or an alkyl group having from 1 to 12 carbon atoms, more preferably a hydrogen atom or a methyl group, and particularly preferably a methyl group.
  • W 1 , W 2 , W 3 and W 4 each independently represents an oxygen atom or NH, and particularly preferably an oxygen atom.
  • Y 1 , Y 2 , Y 3 and Y 4 each independently represents a divalent connecting group and is not particularly restricted in its structure. Specific examples thereof include Connecting groups (Y-l) to (Y-20) shown below. In the structures below, A and B indicate bonds to the left terminal group and the right terminal group in formulae (1) to (4), respectively. Of the structures shown below, (Y-2) and (Y-13) are preferred from the standpoint of ease in synthesis.
  • Z 1 , Z 2 , Z 3 and Z 4 each independently represents a hydrogen atom or a monovalent substituent, and the structure of the substituent is not particularly restricted. Specific examples thereof include an alkyl group, a hydroxy group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group and an amino group. Among them, from the standpoint of enhancing the dispersibility, the substituent having a steric repulsion effect is preferred.
  • the monovalent substituent represented by any of Z 1 to Z 3 is preferably an alkyl group having from 5 to 24 carbon atoms or an alkoxy group having from 5 to 24 carbon atoms and particularly, an alkoxy group having a branched alkyl group having from 5 to 24 carbon atoms or an alkoxy group having a cyclic alkyl group having from 5 to 24 carbon atoms is preferred.
  • the monovalent substituent represented by any of Z 4 is preferably an alkyl group having from 5 to 24 carbon atoms and particularly, a branched alkyl group having from 5 to 24 carbon atoms or a cyclic alkyl group having from 5 to 24 carbon atoms is preferred.
  • n, m, p and q each represents an integer from 1 to 500.
  • each of j and k in formulae (1) and (2) is preferably an integer from 4 to 6, and most preferably 5.
  • R' represents a branched or straight-chain alkylene group.
  • R' in formula (3) is preferably an alkylene group having from 1 to 10 carbon atoms, and more preferably an alkylene group having 2 or 3 carbon atoms.
  • R' in formula (3) two or more R's having different structures may be mixed to use in the dispersing resin.
  • R represents a hydrogen atom or a monovalent organic group and is not particularly restricted in its structure.
  • R is preferably a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, more preferably a hydrogen atom or an alkyl group.
  • the alkyl group is preferably a straight-chain alkyl group having from 1 to 20 carbon atoms, a branched alkyl group having from 3 to 20 carbon atoms or a cyclic alkyl group having from 5 to 20 carbon atoms, more preferably a straight-chain alkyl group having from 1 to 20 carbon atoms, and particularly preferably a straight-chain alkyl group having from 1 to 6 carbon atoms.
  • the structural unit represented by formula (1) is more preferably a structural unit represented by formula (1 A) shown below.
  • the structural unit represented by formula (2) is more preferably a structural unit represented by formula (2A) shown below.
  • X 1 , Y 1 , Z 1 and n have the same meanings as X 1 , Y 1 , Z 1 and n in formula
  • X 2 , Y 2 , Z 2 and m have the same meanings as X 2 , Y 2 , Z 2 and m in formula
  • the structural unit represented by formula (3) is more preferably a structural unit represented by formula (3A) or (3B) shown below.
  • X 3 , Y 3 , Z 3 and p have the same meanings as X 3 , Y 3 , Z 3 and p in formula (3), and preferred ranges are also the same.
  • the numerical value attached to each structural unit indicates the content (% by weight, shown as (wt%)) of the structural unit.
  • the numerical value attached to the repeating unit of the side chain indicates the number of repetitions of the repeating unit.
  • a dispersing agent from the standpoint of enhancing the dispersibility, it is preferred to prepare a dispersion composition using the fine particle of tungsten oxide containing an alkali metal (and, if desired, the other infrared ray blocking agent described above), the dispersing agent and an appropriate solvent and then the dispersion composition is blended with the infrared ray shielding composition.
  • the infrared ray shielding composition according to the invention may or may not contain the dispersing agent, and in the case of containing the dispersing agent, the content thereof in the composition is preferably from 1 to 90 % by weight, more preferably from 3 to 70% by weight, based on the total solid content of the fine particle of tungsten oxide containing an alkali metal in the composition or, in the case of using other infrared ray blocking agent and using an infrared absorbing inorganic pigment as the other infrared ray blocking agent, based on the sum of the total solid content of the fine particle of tungsten oxide containing an alkali metal and the total solid content of the infrared absorbing inorganic pigment in the infrared ray shielding composition.
  • the infrared ray shielding composition according to the invention may contain an ultraviolet absorbing agent.
  • the ultraviolet absorbing agent is incorporated, for example, into an infrared ray shielding composition for solder resist and after forming a photosensitive layer by coating the infrared ray shielding composition on a semiconductor substrate for solid-state imaging device where an alignment mark is provided on the surface, exposure and development are conducted to form a solder resist layer, whereby a solder resist layer capable of satisfying both solving the problem derived from reflected light on the substrate surface described below and ensuring detection performance of the alignment mark by a visible light sensor can be more reliably produced.
  • the substrate surface having provided thereon a photosensitive layer is formed of a material having high light reflectivity, for example, metal
  • the cross-sectional shape of the obtained pattem is liable to become a skirt shape (that is, rectangularity of the cross-sectional shape is liable to be impaired).
  • the exposure amount is suppressed in order to reduce the reflected light, a pattern having a rectangular cross-sectional shape can be hardly formed because of the insufficient exposure amount.
  • the infrared ray shielding composition according to the invention contains the ultraviolet absorbing agent, even when irradiation is performed with an exposure amount necessary to obtain a pattern having a rectangular cross-sectional shape (hereinafter, also referred to as an "adequate exposure amount" sometimes), the ultraviolet absorbing agent absorbs the reflected light and thus, the infrared ray shielding composition containing the ultraviolet absorbing agent according to the invention is suitable for forming the pattem having a rectangular cross-sectional shape.
  • the ultraviolet absorbing agent any compound may be used as long as it satisfies the spectral characteristics described above.
  • the ultraviolet absorbing agent indicates a compound having no function of initiating the polymerization of a polymerizable compound by light or heat (that is, a compound not falling under the category of a polymerization initiator).
  • the term "having no function of initiating the polymerization of a polymerizable compound" as used herein means that even when the ultraviolet absorbing agent receives light or heat energy, it does not generate an active species for initiating the polymerization of a polymerizable compound.
  • the ultraviolet absorbing agent is preferably a compound having no photosensitivity to an ultraviolet ray or visible light (more specifically, light having a wavelength from 300 to 450 nm) and having no thermosensitivity to heat (more specifically, for example, heat from 150 to 250°C).
  • photosensitivity and “thermosensitivity” as used herein mean to exhibit the intended function while accompanying change in the chemical structure by the ultraviolet ray or visible light or heat.
  • the ultraviolet absorbing agent is preferably not only having no function of initiating the polymerization of a polymerizable compound but also having no properly of a sensitizer described below.
  • the term "property of a sensitizer” as used herein means the properly of transferring energy obtained by light absorption of the sensitizer itself to other material (polymerization initiator, for example, the triazine polymerization initiator) and thereby initiating the polymerization.
  • the ultraviolet absorbing agent is preferably a compound having a maximum absorption wavelength in a range from 300 to 430 nm, and more preferably a compound having a maximum absorption wavelength in a range from 330 to 420 nm.
  • the ultraviolet absorbing agent still more preferably has a maximum absorption wavelength at least in one range of (I) range from 340 to 380 nm, (II) range from 380 to 420 nm and (III) range of from 420 to 450 nm.
  • the ultraviolet absorbing agent preferably has a maximum absorption wavelength in the wavelength range (I) described above.
  • the ultraviolet absorbing agent preferably has a maximum absorption wavelength in the wavelength range (II) described above.
  • the ultraviolet absorbing agent preferably has a maximum absorption wavelength in the wavelength range (III) described above.
  • the ultraviolet absorbing agent for example, a salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based or triazine-based ultraviolet absorbing agent can be used.
  • salicylate-based ultraviolet absorbing agent examples include phenyl salicylate, p-octylphenyl salicylate and p-tert-butylphenyl salicylate.
  • benzophenone-based ultraviolet absorbing agent examples include 2,2'-dihydroxy-4-methoxybenzophenone,
  • 2-hydroxy-4-octoxybenzophenone examples include 2-(2' -hydroxy-3 ' ,5 '-di-tert-butylphenyl)-5-chlorobenzotriazole,
  • Examples of the substituted acrylonitrile-based ultraviolet absorbing agent include ethyl 2-cyano-3,3-diphenylacrylate and 2-ethylhexyl 2-cyano-3,3-diphenylacrylate.
  • Examples of the triazine-based ultraviolet absorbing agent include a mono(hydroxyphenyl)triazine compound, for example,
  • DPO diethylamonopnenylsulfonyl pentadienoate-based ultraviolet absorbing agent
  • the ultraviolet absorbing agent is preferably a compound represented by formula (A) shown below.
  • R$i and 3 ⁇ 4 2 each independently represents a hydrogen atom, an alkyl group or an aryl group, or and are combined with each other to represent a nonmetallic atomic group necessary for forming a 5-membered or 6-membered ring. Also, either one of R ⁇ t and 3 ⁇ 4 2 may be combined with the methine group next to the nitrogen atom to form a 5-membered or 6-membered ring.
  • 3 ⁇ 4 and Y 6 i each independently represents a cyano group, -COORa, -CONR63R 64 , -COR63, -S0 2 R63 or -SC ⁇ R ⁇ i ⁇ , and R « and each independently represents a hydrogen atom, an alkyl group or an aryl group.
  • 3 ⁇ 4 and Y 6 i may be combined with each other to form a 5-membered or 6-membered ring.
  • any one of R6i, 3 ⁇ 4 2 , ⁇ and Y 61 may be combined with any one of Rs ⁇ , !1 ⁇ 2, 3 ⁇ 4 and Y 61 in another compound represented by formula (A) to form a dimer.
  • the various ultraviolet absorbing agents may be used individually or in combination of two or more thereof.
  • the infrared ray shielding composition according to the invention may or may not contain the ultraviolet absorbing agent, and in the case of containing the ultraviolet absorbing agent, the content thereof is preferably from 0.001 to 1% by weight, more preferably from 0.01 to 0.3% by weight, based on the total solid content of the infrared ray shielding composition according to the invention.
  • the infrared ray shielding composition according to the invention may contain a sensitizer for the purpose of increasing the radical generating efficiency of the triazine polymerization initiator and making the photosensitive wavelength longer.
  • the sensitizer which can be used in the invention is preferably a compound capable of sensitizing the triazine polymerization initiator described above by an electron transfer mechanism or an energy transfer mechanism.
  • the sensitizer which can be used in the invention includes compounds belonging to compound groups described below and having an absorption wavelength in the wavelength region from 300 to 450 nm.
  • Preferred examples of the sensitizer include compounds belonging to the following compound groups and having an absorption wavelength in the wavelength region from 330 to 450 nm.
  • preferred compounds include a multinuclear aromatic compound (for example, phenanthrene, anthracene, pyrene, perylene, triphenylene or 9,10-dialkoxyanthracene), a xanthene (for example, fluorescein, eosin, erythrosine, Rhodamine B or rose Bengal), a thioxanthone (2,4-diethylthioxanthone, isopropylthioxanthone, diethylthioxanthone or chlorothioxanthone), a cyanine (for example, thiacarbocyanine or oxacarbocyanine), a merocyanine (for example, merocyanine or carbomerocyanine), a phthalocyanine, a thiazine (for example, thionine, methylene blue or toluidine blue), an acridine (for example, acridine orange, chlor
  • the infrared ray shielding composition according to the invention may or may not contain the sensitizer, and in the case of containing the sensitizer, the content thereof is preferably from 0.01 to 10% by weight, more preferably from 0.1 to 2% by weight, based on the total solid content of the infrared ray shielding composition according to the invention.
  • the infrared ray shielding composition according to the invention may further contain a crosslinking agent for the purpose of increasing the strength of the infrared ray shielding film.
  • the crosslinking agent a compound having a crosslinkable group is preferred, and a compound having two or more crosslinkable groups is more preferred.
  • the crosslinkable group suitably include an oxetane group, a cyanate group and those groups described for the crosslinkable group which the alkali-soluble binder may have.
  • an epoxy group, an oxetane group and a cyanate group are preferred.
  • the crosslinking agent is particularly preferably an epoxy compound, an oxetane compound or a cyanate compound.
  • Examples of the epoxy compound which can be suitably used as the crosslinking agent in the invention include an epoxy compound containing at least two oxirane groups per molecule and an epoxy compound having an alkyl group at the ⁇ -position and containing at least two epoxy groups per molecule.
  • Examples of the epoxy compound having at least two oxirane groups per molecule include a bixylenol-type or biphenol-type epoxy compound (for example, YX4000 produced by Japan Epoxy Resin Co., Ltd.) or a mixture thereof, a heterocyclic epoxy compound having an isocyanurate skeleton or the like (for example, TEPIC produced by Nissan Chemical Industries, Ltd.
  • a bixylenol-type or biphenol-type epoxy compound for example, YX4000 produced by Japan Epoxy Resin Co., Ltd.
  • a heterocyclic epoxy compound having an isocyanurate skeleton or the like for example, TEPIC produced by Nissan Chemical Industries, Ltd.
  • an epoxy compound having an alkyl group at the ⁇ -position and containing at least two epoxy groups per molecule can be used.
  • a compound containing an epoxy group substituted with an alkyl group at the ⁇ -position is particularly preferred.
  • epoxy compounds containing at least an epoxy group having an alkyl group at the ⁇ -position all of two or more epoxy groups contained per molecule may be a ⁇ -alkyl-substituted glycidyl group or at least one epoxy group may be a ⁇ -alkyl-substituted glycidyl group.
  • oxetane compound examples include an oxetane resin having at least two oxetanyl groups per molecule.
  • ether compound of a compound having an oxetane group and a compound having a hydroxy group for example, a novolac resin, poly(p-hydroxystyrene), a cardo-type bisphenol, a calixarene, a
  • calixresorcinarene or silsesquioxane examples include a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth)acrylate.
  • bismaleimide compound examples include 4,4'-diphenylmethanebismaleimide, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane and 2,2'-bis[4-(4-maleimidophenoxy)phenyl]propane.
  • cyanate compound examples include a bis A-type cyanate compound, a bis F-type cyanate compound, a cresol novolac-type cyanate compound and a phenol novolac-type cyanate compound.
  • crosslinking agent melamine or a melamine derivative can be used.
  • melamine derivative examples include methylolmelamine and an alkylated methylolmelamine (a compound obtained by etherifying a methylol group with methyl, ethyl, butyl or the like).
  • the crosslinking agents may be used individually or in combination of two or more thereof.
  • the crosslinking agent is preferably melamine or an alkylated memylolmelarnine, more preferably a hexamethylated methylolmelamine, because they have good preservation stability and are effective in increasing the surface hardness of the photosensitive layer or the film strength of the infrared ray shielding film (cured film) itself.
  • the infrared ray shielding composition according to the invention may or may not contain the crosslinking agent, and in the case of containing the crosslinking agent, the content thereof is preferably from 1 to 40% by weight, more preferably from 3 to 20% weight, based on the total solid content of the infrared ray shielding composition according to the invention.
  • the infrared ray shielding composition according to the invention may further contain a curing accelerator for the purpose of accelerating heat curing of the crosslinking agent, for example, an epoxy compound or an oxetane compound.
  • a curing accelerator for the purpose of accelerating heat curing of the crosslinking agent, for example, an epoxy compound or an oxetane compound.
  • the curing accelerator which can be used include an amine compound (for example, dicyandiamide, benzyldimethylamine, 4-(dimemylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine or 4-methyl-N,N-dimethylbenzylamine), a quaternary ammonium salt compound (for example, triethylbenzylammonium chloride), a blocked isocyanate compound (for example, dimethylamine), an imidazole derivative dicyclic amidine compound or salt thereof (for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, l-cyanoethyl-2-phenylimidazole or 1- (2-cyanoethyl)-2-ethyl-4-methylimidazole), a phosphorus compound (
  • triphenylphosphine a guanamine compound (for example, melamine, guanamine, acetoguan amine or benzoguanamine), and an S-triazine derivative (for example,
  • the curing accelerator is preferably melamine or dicyandiamide.
  • the curing accelerators may be used individually or in combination of two or more thereof.
  • the infrared ray shielding composition according to the invention may or may not contain the curing accelerator, and in the case of containing the curing accelerator, the content thereof is preferably from 0.01 to 15% by weight based on the total solid content of the infrared ray shielding composition according to the invention.
  • the infrared ray shielding composition according to the invention may further contain a filler.
  • the filler which can be used in the invention includes a spherical silica surface-treated with a silane coupling agent.
  • the infrared ray shielding composition containing a filler according to the invention is preferred because an infrared ray shielding film having high durability can be obtained (in particular, this effect is remarkable when more severe durability is required of a solder resist, for example, in the case where a metal wiring covered with a solder resist has a high wiring density).
  • the thermal cycle test resistance and preservation stability of the infrared ray shielding composition is increased and, for example, even after passing through a sever atmosphere, for example, the thermal cycle test, the same good profile as that immediately after pattern formation can be maintained.
  • the "spherical" as to the spherical filler is sufficient if the particle is not in an acicular, columnar or amorphous shape but is rounded, and the particle need not be necessarily “perfectly spherical", but a typical "spherical” shape is a "perfectly spherical” shape.
  • the volume average particle size of the primary particle of the filler is not particularly restricted and may be appropriately selected according to the purpose, and is preferably from 0.05 to 3 um, and more preferably from 0.1 to 1 um.
  • the average particle size of the primary particle of the filler is in the range described above, reduction in the processability due to development of thixotropy is suppressed and increase in the maximum particle size is prevented, which is advantageous in that the generation of defect caused by attachment of a foreign material to the infrared ray shielding film (cured film) formed or unevenness of the coated layer is prevented.
  • the volume average particle size of the primary particle of the filler can be measured by a dynamic light scattering particle size distribution measuring device.
  • the filler can be dispersed by using the dispersing agent or binder described above.
  • the alkali-soluble binder polymer having a crosslinkable group in the side chain is particularly preferred from the standpoint of curability.
  • the surface treatment of the filler is described below.
  • the surface treatment of the filler is not particularly restricted and may be appropriately selected according to the purpose, and a treatment of covering silica with a silane coupling agent is preferred.
  • the silane coupling agent used for the surface treatment of the filler is not particularly restricted and may be appropriately selected according to the purpose, and it preferably has at least one functional group selected from an alkoxysilyl group, a chlorosilyl group and an acetoxysilyl group (hereinafter, also referred to as a "first functional group” sometimes) and at least one functional group selected from a (meth)acryloyl group, an amino group and an epoxy group (hereinafter, also referred to as a "second functional group” sometimes).
  • the second functional group is more preferably a (meth)acryloyl group or an amino group, and still more preferably a (meth)acryloyl group. It is advantageous from the standpoint of preservation stability and TCT resistance that the second functional group is a (meth)acryloyl group.
  • the silane coupling agent is not particularly restricted and suitable examples thereof include ⁇ -aminopropyltriethoxysilane, N-(p-ammoemyl)-y-aminopropyltrimethoxysilane,
  • the silane coupling agents may be used individually or in combination of two or more thereof.
  • the surface treatment of the spherical silica with the silane coupling agent may be previously performed for only the spherical silica (in this case, hereinafter, the treatment is also referred to as a "pretreatment" sometimes) or may be performed together with a part or all of other fillers contained in the infrared ray shielding composition.
  • the method for performing the pretreatment is not particularly restricted and examples thereof include a dry method, an aqueous solution method, an organic solvent method and a spraying method.
  • the temperature for performing the pretreatment is not particularly restricted and is preferably from ordinary temperature to 200°C.
  • the catalyst is not particularly restricted and examples thereof include an acid, a base, a metal compound and an organic metal compound.
  • the amount of the silane coupling agent added when performing the pretreatment is not particularly restricted and is preferably from 0.01 to 50 parts by weight, more preferably from 0.05 to 50 parts by weight, per 100 parts by weight of the spherical silica.
  • the amount is in the range described above, the surface treatment sufficient for exhibiting the effect is performed and reduction in the handling property resulting from aggregation of the spherical silica after treatment is suppressed.
  • the silane coupling agent has an action of increasing the adhesion property between the substrate and the photosensitive layer, because the first functional group reacts with an active group on the substrate surface, on the spherical silica surface or in the binder, and further the second functional group reacts with a carboxyl group or an ethylenically unsaturated group in the binder.
  • the silane coupling agent has high reactivity and therefore, when the silane coupling agent itself is added to the infrared ray shielding composition, due to its diffusing action, mainly the second functional group is reacted or deactivated during preservation to cause decrease in shelf life or pot life in some cases.
  • the spherical silica which is pretreated with a silane coupling agent as described above since the diffusing action is suppressed, the problem in the shelf life or pot life is greatly improved and it is possible to make a one-component type composition.
  • the reaction rate between the first functional group of the silane coupling agent and the active group of the spherical silica can be significantly increased in comparison with the case of adding the spherical silica without performing the pretreatment.
  • Examples of the spherical silica surface-treated with a silane coupling agent for use in the invention include FB and SFP Series of Denki Kagaku Kogyo Kabushiki Kaisha, 1-FX of Tatsumori Ltd., HSP Series of Toagosei Co., Ltd., and SP Series of Fuso Chemical Co., Ltd.
  • the infrared ray shielding composition according to the invention may or may not contain the filler and in the case of containing the filler, although the content of the filler is not particularly restricted and may be appropriately selected according to the purpose, it is preferably from 1 to 60% by weight based on the total solid content of the infrared ray shielding composition.
  • the content is in the range described above, a sufficient reduction in the linear expansion coefficient is achieved and the infrared ray shielding film (cured film) formed is prevented from embrittlement and thus, its function as a protective film of wiring is sufficiently exerted when the wiring is formed using the infrared ray shielding film.
  • the infrared ray shielding composition according to the invention may further contain an elastomer.
  • the adhesion property to a conductive layer of a printed wiring board can be more increased and the heat resistance, heat shock resistance, flexibility and toughness of the infrared ray shielding film (cured film) can be more increased.
  • the elastomer which can be used in the invention is not particularly restricted and may be appropriately selected according to the purpose. Examples thereof include a styrene-based elastomer, an olefin-based elastomer, a urethane-based elastomer, a polyester-based elastomer, a polyamide-based elastomer, an acrylic elastomer and a silicone-based elastomer.
  • the elastomer is composed of a hard segment component and a soft segment component, where ordinarily, the former contributes to the heat resistance and strength and the latter contributes to the flexibility and toughness.
  • a polyester-based elastomer is advantageous in view of compatibility with other materials.
  • styrene-based elastomer examples include a styrene-butadiene-styrene block copolymer, a styrene-isoprene-styrene block copolymer, a styrene-ethylene-butylene-styrene block copolymer and a styrene-ethylene-propylene-styrene block copolymer.
  • styrene-based elastomer other than styrene, a styrene derivative, for example, a-methylstyrene, 3-methylstyrene, 4-propylstyrene or 4-cyclohexylstyrene can be used.
  • a styrene derivative for example, a-methylstyrene, 3-methylstyrene, 4-propylstyrene or 4-cyclohexylstyrene can be used.
  • TUFPRENE examples thereof include TUFPRENE, SOLPRENE T, ASAPRENE T and TUFTEC (produced by Asahi Chemical Industry Co., Ltd.), ELASTOMER AR (produced by Aronkasei Co., Ltd.), KRATON G and CALIFLEX (produced by Shell Chemicals Japan Ltd.), JSR-TR, TSR-SIS and DYNARON (produced by JSR Corp.), DENKA STR (produced by Denki Kagaku Kogyo Kabushiki Kaisha), QUINTAC (produced by ZEON Corp.), TPE-SB Series (produced by Sumitomo Chemical Co., Ltd.), RABALON (produced by Mitsubishi Chemical Corp.), SEPTON and HYBRAR (produced by Kuraray Co., Ltd.), SUMIFLEX (produced by Sumitomo Bakelite Co., Ltd.), LEOSTOMER and ACTYMER (produced by Riken Vinyl Industry Co., Ltd.).
  • the olefin-based elastomer is a copolymer of an a-olefin having from 2 to 20 carbon atoms, for example, ethylene, propylene, 1-butene, 1-hexene or 4-methylpentene, and examples thereof include an ethylene-propylene copolymer (EPR) and an ethylene-propylene-diene copolymer (EPDM).
  • EPR ethylene-propylene copolymer
  • EPDM ethylene-propylene-diene copolymer
  • the olefin-based elastomer examples include a copolymer of an a-olefin and a non-conjugated diene having from 2 to 20 carbon atoms, for example, dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylenenorbornene, ethylidenenorbornene, butadiene or isoprene, and an epoxidized polybutadiene.
  • the olefin-based elastomer further includes, for example, a carboxyl-modified NBR obtained by copolymerizing a methacrylic acid with a butadiene-acrylonitrile copolymer.
  • the olefin-based elastomer includes, for example, an ethylene-a-olefin copolymer rubber, an ethylene-a-olefin-non-conjugated diene copolymer rubber, a propylene-a-olefin copolymer rubber and a butene-a-olefin copolymer rubber.
  • olefin-based elastomer examples include MILASTOMER (produced by Mitsui Petrochemical Industries, Ltd.), EXACT (produced by Exxon Chemical Corp.), ENGAGE (produced by Dow Chemical Co.), hydrogenated styrene-butadiene rubber (DYNABON HSBR, produced by JSR Corp.), butadiene-acrylonitrile copolymer (NBR Series, produced by JSR Corp.), crosslinking point-containing butadiene-acrylonitrile copolymer modified with carboxyl group at both terminals (XER Series, produced by JSR Corp.) and epoxidized polybutadiene in which polybutadiene is partially epoxidized (BF- 1000, produced by Nippon Soda Co., Ltd.).
  • the urethane-based elastomer comprises a hard segment composed of a low molecular (short chain) diol and a diisocyanate and a soft segment composed of a high molecular (long chain) diol and a diisocyanate.
  • the high molecular (long chain) diol include polypropylene glycol, polytetramethylene oxide, poly(l,4-butylene adipate), poly(ethylene-l,4-butylene adipate), polycaprolactone, poly(l,6-hexylene carbonate) and poly(l,6-hexylene-neopentylene adipate).
  • the number average molecular weight of the high molecular (long chain) diol is preferably from 500 to 10,000.
  • the low molecular (short chain) diol include ethylene glycol, propylene glycol, 1,4-butanediol and bisphenol A.
  • the number average molecular weight of the short chain diol is preferably from 48 to 500.
  • Specific examples of the urethane-based elastomer include PANDEX T-2185 and T-2983N (produced by Dainippon Ink and Chemicals, Inc.) and MIRACTRAN E790.
  • the polyester-based elastomer is obtained by polycondensing a dicarboxylic acid or a derivative thereof and a diol compound or a derivative thereof.
  • the dicarboxylic acid include an aromatic dicarboxylic acid, for example, terephthalic acid, isophthalic acid or naphthalenedicarboxylic acid, an aromatic dicarboxylic acid formed by substituting for a hydrogen atom of the aromatic ring of the dicarboxylic acid above with a methyl group, an ethyl group, a phenyl group or the like, an aliphatic dicarboxylic acid having from 2 to 20 carbon atoms, for example, adipic acid, sebacic acid or dodecanedicarboxylic acid, and an alicyclic dicarboxylic acid, for example, cyclohexanedicarboxylic acid.
  • the dicarboxylic acids may be used individually or in combination of two or more thereof.
  • Specific examples of the diol compound include an aliphatic diol and an alicyclic diol, for example, ethylene glycol, 1 ,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol or 1,4-cyclohexanediol, bisphenol A, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-3-methylphenyl)propane and resorcin.
  • the diol compounds may be used individually or in combination of two or more thereof.
  • a multi-block copolymer having an aromatic polyester (for example, polybutylene terephthalate) moiety as the hard segment component and an aliphatic polyester (for example, polytetramethylene glycol) moiety as the soft segment component may be used.
  • polyester elastomers of various grades according to the kind, ratio, molecular weight difference or the like of the hard segment and soft segment include HYTREL (produced by Du Pont-Toray Co., Ltd.), PELPRENE (produced by Toyobo Co., Ltd.) and ESPEL (produced by Hitachi Chemical Co., Ltd.).
  • the polyamide-based elastomer comprises a hard segment composed of polyamide and a soft segment composed of polyether or polyester and is roughly classified into two types of a polyether block amide type and a polyether-ester block amide type.
  • Examples of the polyamide include polyamide 6, polyamide 11 and polyamide 12.
  • Examples of the polyether include polyoxyethylene, polyoxypropylene and polytetramethylene glycol.
  • polyamide-based elastomer examples include UBE Polyamide Elastomer (produced by Ube Industries, Ltd.), DAIAMIDE (produced by Daicel-Huels Ltd.), PEBAX (produced by Toray Industries, Inc.), GRILON ELY (EMS-CHEMIE (Japan) Ltd.), NOVAMID (produced by Mitsubishi Chemical Corp.) and GRILAX (produced by Dainippon Ink and Chemicals, Inc.).
  • the acrylic elastomer is obtained by copolymerizing an acrylic acid ester, for example, ethyl acrylate, butyl acrylate, methoxyethyl acrylate or ethoxyethyl acrylate with an epoxy group-containing monomer, for example, glycidyl methacrylate or alkyl glycidyl ether and/or a vinyl monomer, for example, acrylonitrile or ethylene.
  • an acrylic acid ester for example, ethyl acrylate, butyl acrylate, methoxyethyl acrylate or ethoxyethyl acrylate
  • an epoxy group-containing monomer for example, glycidyl methacrylate or alkyl glycidyl ether
  • a vinyl monomer for example, acrylonitrile or ethylene.
  • acrylic elastomer examples include an acrylonitrile-butyl acrylate copolymer, an acrylonitrile-butyl acrylate-ethyl acrylate copolymer and an acrylonitrile-butyl acrylate-glycidyl methacrylate copolymer.
  • the silicone-based elastomer is mainly composed of an organopolysiloxane and classified into a polydimethylsiloxane type, a polymethylphenylsiloxane type and a polydiphenylsiloxane type.
  • An organopolysiloxane partially modified with a vinyl group, an alkoxy group or the like may also be used.
  • Specific examples of the silicone-based elastomer include KE Series (produced by Shin-Etsu Chemical Co., Ltd.), SE Series, CY Series and SH Series (produced by Dow Corning Toray Silicone Co., Ltd.).
  • a rubber-modified epoxy resin can be used.
  • the rubber-modified epoxy resin is obtained by modifying a part or all of epoxy groups of, for example, the bisphenol F-type epoxy resin, bisphenol A-type epoxy resin, salicylaldehyde-type epoxy resin, phenol novolac-type epoxy resin or cresol novolac-type epoxy resin described above, with both-terminal carboxyl group-modified butadiene-acrylonitrile rubber, terminal amino-modified silicone rubber or the like.
  • elastomers from the standpoint of shear adhesion property and heat shock resistance, a butadiene-acrylonitrile copolymer modified with carboxyl group at both terminals, a polyester-based elastomer having a hydroxy group (ESPEL 1612 and 1620, produced by Hitachi Chemical Co., Ltd.) and an epoxidized polybutadiene are preferred.
  • ESPEL 1612 and 1620 produced by Hitachi Chemical Co., Ltd.
  • an epoxidized polybutadiene are preferred.
  • the infrared ray shielding composition according to the invention may or may not contain the elastomer and in the case of containing the elastomer, although the content of the elastomer is not particularly restricted and may be appropriately selected according to the purpose, it is preferably from 0.5 to 30% by weight, more preferably from 1 to 10% by weight, particularly preferably from 3 to 8% by weight, based on the total solid content of the infrared ray shielding composition. It is advantageous that the content is in the preferred range described above because the shear adhesion property and heat shock resistance can be more improved.
  • various surfactants from the standpoint of more improving the coating property.
  • various surfactants for example, a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant or a silicone-based surfactant may be used.
  • the liquid property (particularly, fluidity) of a coating solution prepared from the infrared ray shielding composition can be more improved so that uniformity of the coating thickness and liquid saving property can be more improved.
  • the interfacial tension between the coating surface and the coating solution is reduced, whereby wettability of the coating surface is increased and the coating property onto the coating surface is improved. Therefore, even when a thin layer of approximately several ⁇ is formed using a smaller amount of the coating solution, it is effective from the standpoint that a layer having a uniform thickness with small unevenness in thickness is suitably formed.
  • the fluorine content in the fluorine-based surfactant is preferably from 3 to 40% by weight, more preferably from 5 to 30% by weight, and particularly preferably from 7 to 25% by weight.
  • the fluorine-based surfactant having the fluorine content of the range described above is effective in view of the uniformity of the coating thickness and liquid saving property and also exhibits good solubility in the infrared ray shielding composition.
  • fluorine-based surfactant examples include MEGAFAC F171, MEGAFAC F172, MEGAFAC F173, MEGAFAC F176, MEGAFAC F177, MEGAFAC F141, MEGAFAC F142, MEGAFAC F143, MEGAFAC F144, MEGAFAC R30, MEGAFAC F437, MEGAFAC F475, MEGAFAC F479, MEGAFAC F482, MEGAFAC F554, MEGAFAC F780 and MEGAFAC F781 (produced by DIC Corp.), FLUORAD FC430, FLUORAD FC431 and FLUORAD FC171 (produced by Sumitomo 3M Ltd.), and SURFLON S-382, SURFLON SC-101, SURFLON SC-103, SURFLON SC-104, SURFLON SC-105, SURFLON SC-1068, SURFLON SC-381 , SURFLON SC-383, SURFLON S-393 and SURFLON
  • nonionic surfactant examples include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate and a sorbitan fatty acid ester (for example, PLURONIC L10, L31, L61, L62, 10R5, 17R2 and 25R2 and TETRONIC 304, 701, 704, 901, 904 and 150R1 (produced by BASF) and SOLSPERSE 20000 (produced by Zeneca).
  • PLURONIC L10, L31, L61, L62, 10R5, 17R2 and 25R2 and TETRONIC 304, 701, 704, 901, 904 and 150R1 produced by BASF
  • SOLSPERSE 20000 produced by Zeneca
  • cationic surfactant examples include a phmdocyanine derivative (EFKA-745, produced by Morishita Sangyo K.K.), Organosiloxane Polymer KP341 (produced by Shin-Etsu Chemical Co., Ltd.), a (meth)acrylic acid (co)polymer (POLYFLOW No. 75, No. 90 and No. 95 (produced by Kyoeisha Chemical Co., Ltd.), and W001 (produced by Yusho Co Ltd.).
  • EFKA-745 produced by Morishita Sangyo K.K.
  • Organosiloxane Polymer KP341 produced by Shin-Etsu Chemical Co., Ltd.
  • POLYFLOW No. 75, No. 90 and No. 95 produced by Kyoeisha Chemical Co., Ltd.
  • W001 produced by Yusho Co Ltd.
  • anionic surfactant examples include W004, W005 and W017 (produced by Yusho Co Ltd.).
  • silicone-based surfactant examples include TORAY SILICONE DC3PA, TORAY SILICONE SH7PA, TORAY SILICONE DCllPA, TORAY SILICONE SH21PA, TORAY SILICONE SH28PA, TORAY SILICONE SH29PA, TORAY SILICONE SH30PA and TORAY SILICONE SH8400 (produced by Dow Corning Toray Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460 and TSF-4452 (produced by Momentive Performance Materials Inc.), KP341, KF6001 and KF6002 (produced by Shin-Etsu Silicone Co., Ltd.), and BYK-323 and BYK-330 (produced by Byk-Chemie GmbH).
  • the surfactants may be used individually or in combination of two or more thereof.
  • the infrared ray shielding composition according to the invention may or may not contain the surfactant, and in the case of containing the surfactant, the content thereof is preferably from 0.001 to 1% by weight, more preferably from 0.01 to 0.1% by weight, based on the total solid content of the infrared ray shielding composition according to the invention.
  • Examples of other components which can be used include a heat curing accelerator, a thermal polymerization inhibitor, a plasticizer and a coloring agent (coloring pigment or dye). Further, an adhesion accelerator to the surface of base material, and other auxiliary agents (for example, an electrically conductive particle, a filler, a defoaming agent, a flame retardant, a leveling agent, a release accelerator, an antioxidant, a perfume, a surface tension-controlling agent or a chain transfer agent) may be used in combination.
  • auxiliary agents for example, an electrically conductive particle, a filler, a defoaming agent, a flame retardant, a leveling agent, a release accelerator, an antioxidant, a perfume, a surface tension-controlling agent or a chain transfer agent
  • the properties of the intended solder resist for example, stability, photographic property or physical property of film can be adjusted.
  • thermal polymerization inhibitor Details of the thermal polymerization inhibitor are described, for example, in paragraphs [0101] and [0102] of JP-A-2008-250074.
  • plasticizer Details of the plasticizer are described, for example, in paragraphs [0103] and [0104] of JP-A-2008-250074.
  • the solid content concentration is preferably from 5 to 90% by weight, more preferably from 20 to 80% by weight, and most preferably from 40 to 60% by weight.
  • the use of the infrared ray shielding composition according to the invention is not particularly restricted and examples thereof include a solder resist, an infrared ray shielding film for the back surface of a silicon substrate in a solid-stage imaging device (infrared ray shielding solder resist in a solid-stage imaging device), and an infrared ray shielding film for a waver level lens.
  • the infrared ray shielding composition according to the invention is preferably used for a solder resist or an infrared ray shielding film for the back surface of a silicon substrate in a solid-stage imaging device (infrared ray shielding solder resist in a solid-stage imaging device).
  • the infrared ray shielding composition according to the invention is used for a solder resist or an infrared ray shielding film for the back surface of a silicon substrate in a solid-stage imaging device (infrared ray shielding solder resist in a solid-stage imaging device), in order to form a coating film having a relatively large thickness, the solid content concentration is preferably from 30 to 80% by weight, more preferably from 35 to 70% by weight, and most preferably from 40 to 60% by weight.
  • the viscosity of the infrared ray shielding composition according to the invention is preferably in a range from 1 to 3,000 mPa-s, more preferably in a range from 10 to 2,000 mPa s, and most preferably in a range from 100 to 1,500 mPa s.
  • the viscosity is preferably in a range from 10 to 3,000 mPa-s, more preferably in a range from 500 to 1,500 mPa-s, most preferably in a range from 700 to 1,400 mPa-s, from the standpoint of thick film-forming property and uniform coating property.
  • the invention also relates to a photosensitive layer formed from the infrared ray shielding composition according to the invention. Since the photosensitive layer is formed of the infrared ray shielding composition according to the invention, the photosensitive layer has a high light shielding property in the infrared region and high light transparency in the visible region and is capable of forming an infrared ray shielding film in which the occurrence of cracking is restrained and which exhibits a high adhesion property to a substrate and high exposure sensitivity. Further, by incorporating an alkali-soluble binder into the infrared ray shielding composition according to the invention, a pattern having the desired profile of high rectangularity can be formed through exposure and alkali development.
  • the invention relates to an infrared ray shielding film which is a cured film formed from the infrared ray shielding composition according to the invention.
  • the infrared ray shielding film according to the invention is a cured film which has a high light shielding property in the infrared region and high light transparency in the visible region, in which the occurrence of cracking is restrained and which exhibits a high adhesion property to a substrate and high exposure sensitivity.
  • the infrared ray shielding film according to the invention including a pattern having the desired profile of high rectangularity can be formed.
  • the invention also relates to a pattern forming method comprising, in this order, a step of forming a photosensitive layer using the infrared ray shielding composition according to the invention, a step of pattern-exposing the photosensitive layer to cure the exposed area, and a step of removing the unexposed area by alkali development to form a pattern.
  • the pattern forming method is described in detail below by taking, as an example, a patterned solder resist formed using the infrared ray shielding composition according to the invention.
  • the descriptions relating to the kind and amount of solvent for preparation of a coating solution, the coating method of the coating solution, the thickness of the photosensitive layer, and the exposure step and other steps are not restricted to the solder resist.
  • a case of forming a photosensitive layer (polymerizable composition layer) using the infrared ray shielding composition is described as an example.
  • a photosensitive layer is formed using the infrared ray shielding composition according to the invention.
  • the photosensitive layer is not particularly restricted as long as it is a layer formed from the infrared ray shielding composition.
  • the layer thickness, stack structure and the like can be appropriate selected according to the purpose.
  • the method for forming the photosensitive layer includes a method of dissolving, emulsifying or dispersing the infrared ray shielding composition according to the invention in water or a solvent to prepare a coating solution, coating the coating solution directly and drying the coating.
  • the solvent for the preparation of the coating solution included in the infrared ray shielding composition according to the invention is not particularly restricted and a solvent capable of uniformly dissolving or dispersing each component of the infrared ray shielding composition according to the invention may be appropriately selected according to the purpose.
  • Examples thereof include an alcohol, for example, methanol, ethanol, normal propanol, isopropanol, normal butanol, secondary butanol or normal hexanol, a ketone, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisobutyl ketone, cyclohexanone or cyclopentanone, an ester, for example, ethyl acetate, butyl acetate, normal amyl acetate, methyl sulfate, ethyl propionate, dimethyl phthalate, ethyl benzoate, propylene glycol monomethyl ether acetate (PGMEA, also known as l-methoxy-2-acetoxypropane) or methoxypropyl acetate, an aromatic hydrocarbon, for example, toluene, xylene, benzene or ethy
  • PMEA Propylene glycol monomethyl ether acetate
  • the method of coating the coating solution on a support is not particularly restricted and may be appropriately selected according to the purpose, and examples thereof include a method of coating the coating solution using a spin coater, a slit spin coater, a roll coater, a die coater or a curtain coater.
  • the drying conditions of the coating layer may vary depending on the respective components, the kind of solvent, the amount used and the like, and the drying is ordinarily conducted at temperature approximately from 60 to 150°C for approximately from 30 seconds to 15 minutes.
  • the thickness of the photosensitive layer is not particularly restricted and may be appropriately selected according to the purpose, and is, for example, preferably from 1 to 100 urn, more preferably from 2 to 50 um, and particularly preferably from 4 to 30 um.
  • the method of forming a solder resist pattern using the infrared ray shielding composition according to the invention comprises at least an exposure step, and ordinarily further comprises a developing step in which the conditions are appropriately selected, if desired, and other steps.
  • exposure as used in the invention includes not only exposure to light having various wavelengths but also irradiation with radiation, for example, an electron beam or an X-ray.
  • the exposure step is a step of exposing the photosensitive layer formed from the infrared ray shielding composition through a mask and in the step, only the region irradiated with light is cured.
  • the exposure is preferably performed by the irradiation with radiation and as the radiation usable at the exposure, an electron beam, KrF, ArF, an ultraviolet light, for example, g-line, h-line or i-line, or visible light is preferably used.
  • KrF, g-line, h-line or i-line is preferred.
  • Examples of the exposure system include stepper exposure and exposure with a high-pressure mercury lamp.
  • the exposure amount is preferably from 5 to 3,000 mJ/cm 2 , more preferably from 10 to 2,000 mJ/cm , and most preferably from 50 to 1,000 mJ/cm .
  • an alkali development processing (developing step) is conducted to dissolve the area not irradiated with light in the exposure step, whereby only the photocured area remains and a patterned solder resist having infrared ray shielding property is formed.
  • the developer is preferably an organic alkali developer which does not cause damage on the underlying circuit or the like.
  • the developing temperature is ordinarily from 20 to 40°C and the developing time is from 10 to 180 seconds.
  • an aqueous alkaline solution obtained by diluting an organic alkaline compound for example, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine or l,8-diazabicyclo-[5,4,0]-7-undecene with pure water to have a concentration of ordinarily from 0.001 to 10% by weight, preferably from 0.01 to 1% by weight, is used.
  • washing (rinsing) with pure water is ordinarily conducted after the development.
  • steps are not particularly restricted and can be appropriately selected according to the purpose. Examples thereof include a surface treatment step of substrate, a curing treatment step and a post-exposure step.
  • the curing treatment step is a step of applying a curing treatment to the photosensitive layer having the pattern formed, if desired, after the developing step. By conducting the treatment, the mechanical strength of the infrared ray shielding film which is the cured film is enhanced.
  • the curing treatment step is not particularly restricted and may be appropriately selected according to the purpose, and suitable examples thereof include an entire surface exposing treatment and an entire surface heating treatment.
  • Examples of the method for the entire surface exposing treatment include a method where the entire surface of the stack having the patterned photosensitive layer formed is exposed after the developing step. BY the entire surface exposure, curing of the polymerization components in the infrared ray shielding composition forming the photosensitive layer is accelerated and curing of the infrared ray shielding film which is the cured film is further proceeds to improve the mechanical strength and durability.
  • the apparatus for conducting the entire surface exposure is not particularly restricted and may be appropriately selected according to the purpose, and preferred examples thereof include an UV exposing machine, for example, an ultrahigh-pressure mercury lamp.
  • the method for the entire surface heating treatment includes a method where the entire surface of the stack having the patterned photosensitive layer formed is heated after the developing step. BY the entire surface heating, the film strength of the curing of the infrared ray shielding film which is the cured film is increased.
  • the heating temperature at the entire surface heating is preferably from 120 to 250°C, and more preferably from 140 to 250°C.
  • the heating temperature is 120°C or more, the film strength is increased by the heat treatment, and when the heating temperature is 250°C or less, the resin in the infrared ray shielding composition can be prevented from decomposing to weaken and embrittle the film quality.
  • the heating time in the entire surface heating is preferably from 3 to 180 minutes, and more preferably from 5 to 120 minutes.
  • the apparatus for conducting the entire surface heating is not particularly restricted and may be appropriately selected from known apparatuses according to the purpose, and examples thereof include a dry oven, a hot plate and an IR heater.
  • the patterned resist thus-formed has excellent infrared ray blocking property and thus, its application range is wide. Since the infrared ray shielding composition according to the invention is excellent in the light shielding property in the infrared region and light transparency in the ultraviolet to visible regions, a pattern having an excellent profile is formed and the infrared ray shielding film having the pattern formed has excellent infrared shielding property so that it is useful in the formation of a solder resist for a device with a photodiode having sensitivity to the infrared region, particularly, a solid-state imaging device.
  • the infrared ray shielding composition according to the invention is useful in the formation of not only a solder resist but also an infrared ray shielding film for the back surface of a silicon substrate in a solid-state imaging device or an infrared ray shielding film for a wafer-level lens.
  • the invention also relates to a solid-state imaging device having an infrared ray shielding film formed from the infrared ray shielding composition according to the invention.
  • top each indicates a side farther from a silicon substrate 10
  • bottom each indicates a side closer to the silicon substrate 10.
  • Fig. 1 is a schematic cross-sectional view showing a configuration of a camera module equipped with a solid-state imaging device according to a specific example of the embodiment above.
  • a camera module 200 shown in Fig. 1 is connected to a circuit substrate 70 as a mounting substrate through a solder ball 60 as a connection member.
  • the camera module 200 is configured to comprise a solid-state imaging device substrate 100 having an image-forming device unit on a first major surface of a silicon substrate, a glass substrate 30 (light-transmitting substrate) disposed on the upper side of the first major surface of the solid-state imaging device substrate 100, an infrared cut filter 42 disposed above the glass substrate 30, a lens holder 50 having an imaging lens 40 and being disposed above the glass substrate 30 and the infrared cut filter 42, and a light-shielding and electromagnetic shield 44 disposed to surround the periphery of the solid-state imaging device substrate 100 and the glass substrate 30.
  • Respective members are adhered using adhesives 20, 41, 43 and 45.
  • incident light hv from the outside sequentially passes through the imaging lens 40, the infrared cut filter 42 and the glass substrate 30 and reaches the imaging device unit of the solid-state imaging device substrate 100.
  • the camera module 200 is connected to a circuit board 70 through a solder ball 60 (connection material) on the second major surface side of the solid-state imaging device substrate 100.
  • Fig. 2 is an enlarged cross-sectional view of the solid-state imaging device substrate 100 in
  • the solid-state imaging device substrate 100 is configured to comprise a silicon substrate 10 as a base material, an imaging device 12, an interlayer insulating film 13, a base layer 14, a red color filter 15R, a green color filter 15G, a blue color filter 15B, an overcoat 16, a microlens 17, a light shielding film 18, an insulating film 22, a metal electrode 23, a solder resist layer 24, an internal electrode 26 and a device surface electrode 27.
  • the solder resist layer 24 may be omitted.
  • the configuration on the first major surface side of the solid-state imaging device substrate 100 is mainly described below.
  • an imaging device unit where a plurality of imaging devices 12, for example, CCD and CMOS are two-dimensionally arrayed is provided on the first major surface side of a silicon substrate 10 which is the base material of the solid-state imaging device substrate 100.
  • An interlayer insulating film 13 is formed on the imaging device 12 in the imaging device unit, and a base layer 14 is formed on the interlayer insulating film 13. Further, a red color filter 15R, a green color filter 15G and a blue color filter 15B (hereinafter, these are collectively referred to as a "color filter 15" sometimes) corresponding to respective imaging devices 12 are disposed on the base layer 14.
  • a light shielding film not shown may be provided in the boundaries of the red color filter 15R, the green color filter 15G and the blue color filter 15B and in the periphery of the imaging device unit.
  • the light shielding film can be produced, for example, using a known black color resist.
  • An overcoat 16 is formed on the color filter 15, and a microlens 17 corresponding to the imaging device 12 (color filter 15) is formed on the overcoat 16.
  • a peripheral circuit (not shown) and an internal electrode 26 are provided, and the internal electrode 26 is electrically connected to the imaging device 12 through the peripheral circuit.
  • a device surface electrode 27 is formed on the internal electrode 26 through an interlayer insulating film 13.
  • a contact plug (not shown) for electrically connecting these electrodes is formed.
  • the device surface electrode 27 is used for voltage application and signal reading though the contact plug and the internal electrode 26.
  • a base layer 14 is formed on the device surface electrode 27.
  • An overcoat 16 is formed on the base layer 14.
  • the base layer 14 and the overcoat 16 formed on the device surface electrode 27 are opened to form a pad opening and to expose a part of the device surface electrode 27.
  • an adhesive 20 is provided in the periphery of the imaging device part, and the solid-state imaging device substrate 100 and the glass substrate 30 are adhered through the adhesive 20.
  • the silicon substrate 10 has a through-hole penetrating the silicon substrate 10, and a penetrating electrode which is a part of the metal electrode 23 is provided in the through-hole.
  • the imaging device unit and the circuit board 70 are electrically connected by the penetrating electrode.
  • an insulating film 22 is formed from the second major surface to the inner wall of the through-hole.
  • a metal electrode 23 patterned to extend from the region on the second major surface of the silicon substrate 10 to the inside of the through hole is provided.
  • the metal electrode 23 is an electrode for connecting the imaging device unit in the solid-state imaging device substrate 100 and the circuit board 70.
  • the penetrating electrode is the portion formed inside the through hole of the metal electrode 23.
  • the penetrating electrode penetrates the silicon substrate 10 and a part of the interlayer insulating film and reaches the lower side of the internal electrode 26 to be electrically connected to the internal electrode 26.
  • solder resist layer 24 (protective insulating film) covering the second major surface on which the metal electrode 23 is formed and having an opening to expose a part of the metal electrode 23 is provided.
  • a light shielding film 18 covering the second major surface on which the solder resist layer 24 is formed and having an opening to expose a part of the metal electrode 23 is provided.
  • an infrared ray shielding solder resist layer where the light shielding film 18 and the solder resist layer 24 together form a single layer may be formed from the infrared ray shielding composition according to the invention, or (2) the light shielding film 18 and the solder resist layer 24 are separate layers and the light shielding film 18 may be formed from the infrared ray shielding composition according to the invention (in this case, the solder resist layer may be formed using a known solder resist composition).
  • the light shielding film 18 is patterned to cover a part of the metal electrode 23 and to expose the remaining portion, it may be patterned to expose the entirety of the metal electrode 23 (the same applies to the patterning of the solder resist layer 24).
  • solder resist layer 24 may be omitted and a light shielding film 18 may be formed directly on the second major surface where the metal electrode 23 is formed.
  • a solder ball 60 as a connection member is provided on the exposed metal electrode 23, and the metal electrode 23 of the solid-state imaging device substrate 100 and a connection electrode not shown of the circuit board 70 are electrically connected through the solder ball 60.
  • each part other than the light shielding film 18 of the solid-state imaging device substrate 100 can be formed by a known method, for example, a method described in paragraphs [0033] to [0068] of JP-A-2009-158863 or a method described in paragraphs [0036] to [0065] of JP-A-2009-99591.
  • the light shielding film 18 can be formed by the method of producing the infrared ray shielding film according to the invention described above.
  • the interlayer insulating film 13 is formed as an Si0 2 film or an SiN film, for example, by sputtering or CVD (chemical vapor deposition).
  • the color filter 15 is formed, for example, by photolithography using a known color resist.
  • the overcoat 16 and the base layer 14 are formed, for example, by photolithography using a known resist for forming an organic interlayer film.
  • the microlens 17 is formed, for example, by photolithography using a styrene resin or the like.
  • the layer is preferably formed using the infrared ray shielding composition according to the invention.
  • the solder resist layer 24 is a separate layer from the light shielding film 18, the solder resist layer 24 is preferably formed, for example, by photolithography using a known solder resist containing a phenolic resin, a polyimide resin or an amine resin.
  • the solder ball 60 is formed, for example, as Sn-Pb (eutectic), 95Pb-Sn (high-lead high melting point solder) or Pb-free solder by using Sn-Ag, Sn-Cu, Sn-Ag-Cu or the like.
  • the solder ball 60 is formed, for example, as a sphere having a diameter from 100 to 1,000 um (preferably a diameter from 150 to 700 um).
  • the internal electrode 26 and the device surface electrode 27 are formed, for example, as a metal electrode, for example, Cu by CMP (chemical mechanical polishing) or photolithography and etching.
  • the metal electrode 23 is formed, for example, as a metal electrode, for example, Cu, Au, Al, Ni, W, Pt, Mo, Cu compound, W compound or Mo compound by sputtering, photolithography, etching or electrolytic plating.
  • the metal electrode 23 may have a sing- layer configuration or a multilayer configuration consisting of two or more layers.
  • the thickness of the metal electrode 23 is, for example, from 0.1 to 20 ⁇ (preferably from 0.1 to 10 um).
  • the silicon substrate 10 is not particularly restricted and a silicon substrate thinned by grinding the back surface of the substrate may be used.
  • the thickness of the substrate is not restricted and a silicon wafer having a thickness of 20 to 200 um (preferably from 30 to 150 um) is used.
  • the through-hole of the silicon substrate 10 is formed, for example, by photolithography or RIE (reactive ion etching).
  • the solid-state imaging device substrate 100 as a specific example of the embodiment above is described with reference to Fig. 1 and Fig. 2, but the embodiment above is not restricted to the configuration mode of Fig. 1 and Fig. 2, and the configuration of the device substrate is not particularly restricted as long as it is a configuration having a metal electrode and a light shielding film on the back surface side.
  • Fig. 3 is a plan view showing one example of the wafer-level lens array having a plurality of wafer-level lenses.
  • the wafer-level lens array comprises a substrate 410 and lenses 412 arrayed on the substrate 410.
  • a plurality of lenses 412 are two-dimensionally arrayed with respect to the substrate 410, they may be one-dimensionally arrayed.
  • Fig. 4 is a cross-sectional view along the line A-A in Fig. 3.
  • a light shielding film 414 for preventing light permeation from portions other than the lens 412 is provided between the plurality of lenses 412 arrayed on the substrate 410.
  • the wafer-level lens is composed of one lens 412 present on the substrate 410 and the light shielding film 414 provided in the circumferential edge part of the lens.
  • the infrared ray shielding composition according to the invention is used for the formation of the light shielding film 414.
  • a wafer-level lens array where a plurality of lenses 412 are two-dimensionally arrayed with respect to the substrate 410 as shown in Fig. 3 is described below as an example.
  • the lens 412 is ordinarily composed of the same material as the substrate 410 and is a lens integrally molded on the substrate 410 or a lens molded as a separate structure and fixed on the substrate.
  • the wafer-level lens is not restricted to the embodiment and may take various embodiments, for example, a multilayer structure or a lens module separated by dicing.
  • the material for forming the lens 412 examples include glass. Since there is a wide variety of glass and glass having a high refractive index can be selected, the glass is suitable as a material for a lens intended to have a large power. Also, the glass is excellent in the heat resistance and has an advantage of withstanding the reflow mounting in an imaging unit or the like.
  • the material for forming the lens 412 include a resin.
  • the resin is excellent in the processability and suitable to simply and inexpensively form a lens face by using a mold or the like.
  • an energy curable resin is preferably used for the formation of the lens 412.
  • the energy curable resin may be either a resin which is cured by heat or a resin which is cured by irradiation with an actinic energy ray (for example, irradiation with heat, an ultraviolet ray or an electron beam).
  • any known energy curable resin may be used and in consideration of reflow mounting in an imaging unit, a resin having a relatively high softening point, for example, a softening point of 200°C or more, is preferred and a resin having a softening point of 250°C or more is more preferred.
  • a silica filler (AEROSIL 50, produced by Nippon Aerosil Co., Ltd., particle size: 30 nm)
  • 92.9 parts by weight of an alkali-soluble resin (ACA230AA, produced by Daicel-Cytec Co. Ltd., weight average molecular weight: 14,000 (value measured by a GPC method and calculated in terms of polystyrene), solid content: 50% by weight, solvent: PGME) and 0.3 parts by weight of melarnine were mixed and the mixture was dispersed in Motor Mill M-50 (produced by Eiger Ltd.) using zirconia beads having a diameter of 1.0 mm at a peripheral speed of 9 m/s for 1.5 hours to prepare Filler dispersion 1.
  • Motor Mill M-50 produced by Eiger Ltd.
  • compositions shown below were mixed and filtered to prepare an infrared ray shielding composition for Example 1.
  • the solid state concentration of the infrared ray shielding composition for Example 1 was 47% by weight.
  • Light shielding particle 18.5% by weight dispersion of YMF-02 19.13 parts by weight (produced by Sumitomo Metal Mining Co., Ltd., cesium tungsten oxide
  • Polymerizable compound A-DCP (produced by Shin-Nakamura 4.63 parts by weight Chemical Co., Ltd., tricyclodecane dimethanol diacrylate (difunctional
  • Triazine photopolymerization initiator Compound A 1.10 parts by weight
  • KAYACURE DETX-S thioxanthone compound, 0.38 parts by weight produced by Nippon Kayaku Co., Ltd.
  • Ultraviolet absorbing agent DPO (produced by FUJIFILM 0.07 parts by weight Finechemicals Co., Ltd.)
  • Silane coupling agent KBM-503 (produced by Shin-Etsu Silicone 2.10 parts by weight Co., Ltd.)
  • the infrared ray shielding compositions for Examples 2 to 5 were prepared in the same manner as in the infrared ray shielding composition for Example 1 except for replacing the triazine photopolymerization initiator (Compound A) with Compounds B to E, respectively.
  • the solid state concentration of each of the infrared ray shielding compositions for Examples 2 to 5 was 47% by weight.
  • the infrared ray shielding composition for Example 6 was prepared in the same manner as in the infrared ray shielding composition for Example 1 except that 58.39 parts by weight of Filler dispersion 1 was replaced with 72.10 parts by weight of Filler dispersion 2 and that the amount of PGMEA was changed from 14.10 pars by weight to 0.39 pars by weight.
  • the solid state concentration of the infrared ray shielding composition for Example 6 was 43% by weight.
  • the infrared ray shielding compositions for Examples 7 to 10 were prepared in the same manner as in the infrared ray shielding composition for Example 6 except for replacing the triazine photopolymerization initiator (Compound A) with Compounds B to E, respectively.
  • the solid state concentration of each of the infrared ray shielding compositions for Examples 7 to 10 was 43% by weight.
  • the infrared ray shielding composition for Comparative Example 1 was prepared in the same manner as in the infrared ray shielding composition for Example 1 except for replacing the light shielding particle YMF-02 with the titanium black dispersion shown below.
  • the solid state concentration of the infrared ray shielding composition for Comparative Example 1 was 47% by weight.
  • titanium oxide having a particle size of 15 nm (MT-150A, produced by Tayca Corp.), 25 g of a silica particle having a BET surface area of 300 m 2 /g (AEROPERL 300/30, produced by Evonik Industries) and 100 g of DISPERBYK 190 (produced by BYK-Chemie GmbH) were weighed and thereto added 71 g of ion exchanged water.
  • the resulting mixture was treated using a MAZERUSTAR KK-400W (produced by Kurabo Industries Ltd.) at an orbital rotation rate of 1,360 rpm and a spin rotation rate of 1,047 rpm for 20 minutes to obtain a uniform aqueous mixture.
  • the aqueous mixture was charged into a quartz vessel and heated using a small rotary kiln (produced by Motoyama Co., Ltd.) under an oxygen atmosphere at 920°C.
  • the atmosphere was substituted with nitrogen and then an ammonia gas was introduced at the same temperature as above at a rate of 100 irnVmin for 5 hours to conduct a nitrogen reduction treatment.
  • the collected powder was ground in a mortar to obtain Titanium black A in the powder form.
  • V-601 dimethyl 2,2-azobis(2-methyl propionate) (V-601, produced by Wako Pure Chemical Industries, Ltd.) was added thereto, followed by stirring with heating at 75°C for 2 hours. After 2 hours, 0.2 g of V-601 was further added, followed by stirring with heating for 3 hours to obtain a 30% by weight
  • composition ratio, acid value and weight average molecular weight (Mw) of Dispersing agent 1 were shown below.
  • the weight average molecular weight was measured by gel permeation chromatography (GPC) and calculated in terms of polystyrene.
  • the GPC was conducted using HLC-8020GPC (produced by Tosoh Corp.) with TSKGEL SUPER HZM-H, TSKGEL SUPER HZ4000 and TSKGEL SUPER HZ200 (produced by Tosoh Corp.) as columns.
  • Composition 1 The components in Composition 1 shown below were mixed using a stirrer (EUROSTAR, produced by IKA Works, Inc.) for 15 minutes to obtain a dispersion.
  • a stirrer (EUROSTAR, produced by IKA Works, Inc.) for 15 minutes to obtain a dispersion.
  • Titanium black A produced above 25 parts by weight
  • Dispersing agent Dispersing agent 1 prepared above (30% by weight 25 parts by weig solution)
  • the dispersion thus obtained was subjected to a dispersion treatment under the conditions described below using an ULTRA APEX MILL UAM015 (produced by Kotobuki Industries Co., Ltd.) to obtain a titanium black dispersion (solid content concentration: 18.0% by weight).
  • the particle size of titanium black dispersion indicating a maximum value in the particle size distribution was 19 nm.
  • Amount of mixed solution to be dispersed 500 g
  • Circulating flow rate (pump feed amount) 13 kg/hour
  • Cooling water tap water
  • the infrared ray shielding composition for Comparative Example 2 was prepared in the same manner as in the infrared ray shielding composition for Example 6 except for replacing the triazine polymerization initiator (Compound A) with an a-aminoketone polymerization initiator (IRGACURE 907, produced by BASF Japan Ltd.).
  • the solid state concentration of the infrared ray shielding composition for Comparative Example 2 was 43% by weight.
  • Holes each having a diameter of 50 um and a depth of 70 ⁇ were formed in a silicon wafer, and a coating condition for forming a layer having a thickness of 30 um on the silicone wafer having no hole was determined.
  • the infrared ray shielding composition described above was spin-coated under the condition determined above, and subjected to a pre-baking treatment at 100°C for 120 seconds, an ultraviolet curing treatment and a post-baking treatment at 150°C for one hour.
  • the hole portion of the substrate thus-obtained was photographed using a crosssectional SEM and the presence or absence of cracking was visually evaluated.
  • Ranking was conducted using five grades (5 to 1) based on the evaluation criteria shown below. The rank 4 or higher was considered to be acceptable.
  • a coating condition for forming a layer having a thickness of 10 um on a silicone wafer was determined, and the infrared ray shielding composition described above was spin-coated under the condition determined above and subjected to a pre-baking treatment at 100°C for 120 seconds, an ultraviolet curing treatment and puddle development using an aqueous 2.38% by weight tetramethylammonium hydroxide solution at 25 °C for 40 seconds. Then, the substrate was rinsed with a spin shower, washed further with pure water and subjected to a post-baking treatment at 150°C for one hour.
  • the substrate was allowed to stand under conditions of temperature of 110°C and humidity of 100% for 7 days, returned to room temperature (27°C), cut by a cutter to form 100 cross hatchings wherein the size of one cross hatching is 1 mm x 1 mm and a number of the cross hatchings which was not peeled off was counted.
  • Ranking was conducted using five grades (5 to 1) based on the evaluation criteria shown below. The rank 3 or higher was considered to be acceptable.
  • Each of the infrared ray shielding compositions for Examples 1 to 10 and Comparative Examples 1 and 2 was coated on a silicone wafer by a spin coating method so as to have a layer thickness of 25 um and dried on a hot plate at 120°C for 2 minutes to obtain a photosensitive layer.
  • the photosensitive layer was subjected to single entire surface exposure using an i-line exposure device in an amount of 1,000 mJ.
  • the exposed photosensitive layer was subjected to puddle development using N-methyl-2-pyrrolidone (NMP) at 25°C for 40 seconds, rinsed with a spin shower and washed further with pure water.
  • NMP N-methyl-2-pyrrolidone
  • the rate of thickness decrease was not more than 5%.
  • the rate of thickness decrease was 5% or more but not more than 10%.
  • the rate of thickness decrease was 10% or more but not more than 20%.
  • the rate of thickness decrease was 20% or more but not more than 30%.
  • each of the infrared ray shielding compositions for Examples 1 to 5 and Comparative Example 1 was coated on a silicone wafer by a spin coating method so as to have a layer thickness of 25 um and dried on a hot plate at 120°C for 2 minutes to obtain a photosensitive layer.
  • the photosensitive layer was irradiated using an i-line stepper through a photomask containing a circular pattern having a diameter of 300 um with changing an exposure amount in steps of 50 mJ/cm in a range from 50 to 2,000 mJ/cm .
  • the exposed photosensitive layer was subjected to puddle development using an aqueous 2.38% by weight tetramethylammonium hydroxide solution at 25°C for 60 seconds, rinsed with a spin shower and washed further with pure water to obtain an infrared ray shielding solder resist pattern.
  • a minimum exposure amount (mJ/cm 2 ) for obtaining a circle pattern having a diameter of 300 ⁇ when the development step was conducted for 60 seconds (pattern exposure sensitivity) was measured. As the numerical value is smaller, the pattern exposure sensitivity is better.
  • the evaluation was conducted according to the criteria shown below.
  • the minimum exposure amount was not more than 200 mJ/cm 2 .
  • the minimum exposure amount was more than 200 mJ/cm 2 but not more than 250 mJ/cm 2 .
  • the minimum exposure amount was more than 250 mJ/cm 2 but not more than 300 mJ/cm 2 .
  • the minimum exposure amount was more than 300 mJ/cm 2 but not more than 350 mJ/cm 2 .
  • the minimum exposure amount was more than 350 mJ/cm 2 .
  • the pattern was formed on the substrate with sufficient adhesion property and the cross-section of the pattern showed a good rectangular shape.
  • the pattern was formed on the substrate with sufficient adhesion property but the cross-section of the pattern did not show a good rectangular shape.
  • the pattern was formed on the substrate with sufficient adhesion property but the cross-section of the pattern had an undercut profile and did not show a rectangular shape.
  • the infrared ray shielding composition was spin-coated on a glass substrate under the conditions described above to form a coating of a photosensitive layer having a layer thickness of 25 urn and the transmittance at a wavelength of 1,200 nm of the coating was measured using UV-VIS-NIR Spectrophotometer UV-3600 (produced by Shimadzu Corp.). As the transmittance is smaller, the infrared shielding property is more excellent.
  • the evaluation was conducted according to the criteria shown below.
  • the transmittance is not more than 2%.
  • the transmittance is more than 2% but not more than 3%.
  • the transmittance is more than 3% but not more than 5%.
  • the transmittance is more than 5% but not more than 10%.
  • the transmittance is more than 10%.
  • the transmittance at a wavelength of 550 nm of the coating was measured using UV-VIS-NIR Spectrophotometer UV-3600 (produced by Shimadzu Corp.). As the numerical value is larger, the visible light transparence is more excellent. The evaluation was conducted according to the criteria shown below.
  • the transmittance is not less than 30%.
  • the transmittance is less than 30% but not less than 25%.
  • the transmittance is less than 25% but not less than 20%.
  • the transmittance is less than 20% but not less than 15%.
  • Comparative Example 1 using titanium black as the infrared ray shielding agent exhibits the occurrence of many crackings, is inferior in the adhesion property to the substrate and film exposure sensitivity, and, in particular, is extremely inferior in the visible light transparence. It is also found that in the case of the pattern formation, Comparative Example 1 is inferior in the pattern exposure sensitivity and pattern profile.
  • Examples 1 to 5 using the cesium tungsten oxide particle as the infrared ray shielding agent and the triazine polymerization initiator exhibit no or small occurrence of cracking and are excellent in any of the adhesion property to the substrate, film exposure sensitivity, infrared ray shielding property and visible light transparence. It is also found that in the case of the pattern formation, Examples 1 to 5 are excellent in the pattern exposure sensitivity and pattern profile.
  • Comparative Example 2 using the cesium tungsten oxide particle as the infrared ray shielding agent and the polymerization initiator other than the triazine polymerization initiator is excellent or in the acceptable level in the adhesion property to the substrate, infrared ray shielding property and visible light transparence, but is inferior in the occurrence of cracking and film exposure sensitivity.

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Abstract

The invention is directed to an infrared ray shielding composition containing a fine particle of tungsten oxide containing an alkali metal, a triazine polymerization initiator and a polymerizable compound, a photosensitive layer formed from the infrared ray shielding composition, an infrared ray shielding film formed from the infrared ray shielding composition, a solid-state imaging device including a substrate having an imaging device unit formed on one surface of the substrate and the infrared ray shielding film provided on other surface side of the substrate, and a pattern forming method including, in the following order: forming the photosensitive layer; pattern-exposing the photosensitive layer to cure an exposed area; and removing an unexposed area by alkali development to form a pattern.

Description

DESCRIPTION
Title of Invention
INFRARED RAY SHIELDING COMPOSITION, INFRARED RAY SHIELDING FILM, PATTERN FORMING METHOD AND SOLID-STATE IMAGING DEVICE
Technical Field
The present invention relates to an infrared ray shielding composition, an infrared ray shielding film, a pattern forming method and a solid-state imaging device, Particularly, it relates to an infrared ray shielding composition suitably used for forming a solder resist, an infrared ray shielding film, a pattern forming method and a solid-state imaging device.
Background Art
As to a method of forming a permanent pattern, for example, a solder resist, there is known, for example, a method where a photosensitive layer is formed on a silicon wafer on which a permanent pattern is formed, a silicon wafer having wiring thereon or a base material, for example, a copper clad laminate, and the photosensitive layer of the stack is exposed to light, after the exposure the photosensitive layer is developed to form a pattern and then subjected to a curing treatment or the like, thereby forming the permanent pattern.
The formation of permanent pattern is also applied to a package substrate interposed between a semiconductor chip and a printed board. As to the package substrate, in recent years, higher density packaging is required, and decrease in the wiring pitch and increase in the strength, improvement in the insulating property, decrease in the film thickness and the like of a solder resist layer are proceeding. Also, reduction in the via diameter, increase in the exposure sensitivity and from the standpoint of mounting, a rectangular pattern profile by development are required.
On the other hand, a solid-state imaging device (image sensor) used in a cellular phone, a digital camera, a digital video, a monitoring camera or the like is a photoelectric conversion device having an integrated circuit formed using the production technique of a semiconductor device. In recent years, with decrease in size and weight of a cellular phone or a digital camera, the solid-state imaging device is required to be more downsized.
For downsizing the solid-state imaging device, a technique of applying a through electrode and decreasing thickness of a silicon wafer has been proposed (see, for example, JP-A-2009-194396 (the term "JP-A" as used herein means an "unexamined published Japanese patent application")). The downsizing can be realized by polishing the silicon wafer to decrease the thickness thereof, but due to the decrease in the thickness of silicon wafer, light having a wavelength of 800 nm or more is liable to be transmitted, although the light shielding property of light having a wavelength of 800 nm or less is maintained. Since a photodiode used in the solid-state imaging device also reacts with light having a wavelength from 800 to 1,200 nm, it has been found that a new problem arises in that the image quality is deteriorated based on the transmission of light having a wavelength of 800 nm or more.
The solid-state imaging device has a configuration in that a color filter and a lens are provided adjacent to one side of a photodiode, an infrared cut filter is present in the vicinity of the color filter or lens to block light having a wavelength from 800 to 1,200 nm, and a metal wiring, a solder resist and the like are present on the opposite side of the color filter. The space between the metal wirings is filled with the solder resist in many cases, but there is a problem in that infrared light, for example, leakage light intruding into the inside of a cellular phone, a digital camera or the like cannot be blocked by the solder resist. To cope with the problem, heretofore, a technique of further providing an infrared ray shielding layer on the outer side of the solder resist which is poor in the infrared ray shielding property to ensure the infrared ray shielding property has been employed. However, since a height difference due to the wiring or the like is ordinarily present on the solder resist, it is difficult to coat an infrared ray shielding layer material in a uniform thickness on a substrate surface having the height difference, and when a thin portion exits, a problem arises in that light is transmitted therethrough.
In order to provide an infrared ray shielding layer only in the desired portion, the composition preferably exhibits photosensitivity and has a photolithography performance enabling patterning by exposure. The light shielding photosensitive composition having a photolithography performance includes a black resist containing carbon black used for the formation of an LCD color filter. The carbon black has a high light shielding property in the visible region but exhibits a low light shielding property in the infrared region and when it is attempted to apply such a black resist as a solder resist, if carbon black is added in an amount large enough to ensure the required light shielding property in the infrared region, this causes a problem in that the light shielding property in the visible region becomes excessively high, light having a shorter wavelength than the visible region, which is usually used at the exposure by a high-pressure mercury lamp, KrF, ArF or the like in the image formation, is also blocked so that the photocurability is not sufficiently obtained and excellent pattern cannot be obtained through a development step using an alkali developer.
Also, at present, since an infrared ray shielding layer is separately provided after forming a solder resist by a coating method, in the formation of solder resist and the formation of infrared ray shielding layer, steps, for example, coating, exposure, development and post-heating must be performed plural times to cause a cumbersome process and a rise in the cost and thus, improvements are desired.
Therefore, it has been attempted to impart a light shielding property to the solder resist itself and, for example, a black solder resist composition containing a black coloring agent, a coloring agent other than black and a polyfunctional epoxy compound has been proposed (see, for example, JP-A-2008-257045). However, the composition is characterized in that the content of the black coloring agent is kept low by using a coloring agent other than black in combination and is practically insufficient from the standpoint of light shielding property in the infrared region.
Summary of Invention
For the purpose of detecting the position of a semiconductor substrate by a visible light sensor in the process of producing a solid-state imaging device, an alignment mark of a convex form is often provided at the predetermined position on the surface on the metal wiring and solder resist side (that is, the surface opposite the color filter or lens) of a semiconductor substrate of a solid-state imaging device.
In the configuration where a black coloring agent is contained in the solder resist composition for imparting a light shielding property to the solder resist itself, for example, as in JP-A-2008-257045, when the alignment mark is covered with a solder resist layer, maybe due to the thickness of the solder resist layer, a problem arises in that a trouble that the alignment mark is not detected by the visible light sensor is liable to occur.
Under these circumstances, an infrared ray shielding composition having a high light shielding property in the infrared region, high light transparency in the visible region and high exposure sensitivity and capable of forming a pattern of high rectangularity by development is demanded at present.
Further, in the application of through electrode for downsizing the solid-state imaging device as described above, a technique of providing through holes in a semiconductor substrate, for example, a silicon wafer (Through Si Via: TSV) is known. When metal is wired on the substrate provided with the through holes and it is covered with a solder resist layer, a problem arises in that cracking or peeling of the solder resist occurs in the concave region of the metal wiring derived from the through hole.
A technique of using a layer containing an inorganic near infrared ray absorbing agent as a near infrared ray absorbing layer for an image display device is disclosed in JP-A-2009-205029 and, for example, a coating solution for forming near infrared ray absorbing layer containing a polymerizable compound, a polymerization initiator and a near infrared ray absorbing agent is disclosed in the example thereof, but an infrared ray shielding composition capable of forming a solder resist layer in which the occurrence of cracking is restrained and which exhibits a high adhesion property to a substrate so as to hardly cause the peeling is not described. Thus, such an infrared ray shielding composition is demanded at present.
The present invention has been made under these circumstances, and the problem of the invention is to solve those various conventional problems and achieve the objects described below.
Specifically, an object of the invention is to provide an infrared ray shielding composition having a high light shielding property in the infrared region and high light transparency in the visible region and being capable of forming an infrared ray shielding film in which the occurrence of cracking is restrained and which exhibits a high adhesion property to a substrate and high exposure sensitivity, and an infrared ray shielding film, a pattern forming method and a solid-state imaging device each using the composition.
The means for solving the problem above is specifically described below.
(1) An infrared ray shielding composition containing a fine particle of tungsten oxide containing an alkali metal, a triazine polymerization initiator and a polymerizable compound.
(2) The infrared ray shielding composition as described in (1) above, wherein the triazine polymerization initiator is represented by formula (T) shown below.
Figure imgf000005_0001
sents a halogen-substituted hydrocarbon group, a hydrogen atom, a halogen atom, a dialkylamino group, an alkyl group, an alkoxy group or a cyano group; Y1, which is not present when 1 is 0, represents an ethenylene group or an -NH- group when 1 is 1; B1 and B2 each independently represents an aromatic ring group which may have a substituent; and 1 and m each independently represents any integer selected from 0, 1 and 2.
(3) The infrared ray shielding composition as described in (2) above, wherein X1 and X2 in formula (T) each independently represents a halogen-substituted hydrocarbon group.
(4) The infrared ray shielding composition as described in (2) or (3) above, wherein an
1
aromatic ring constituting the aromatic ring group for B or B in formula (T) is a benzene ring.
(5) The infrared ray shielding composition as described in any one of (1) to (4) above, which further contains an alkali-soluble binder.
(6) The infrared ray shielding composition as described in (5) above, wherein the alkali-soluble binder has an acid group.
(7) The infrared ray shielding composition as described in (5) or (6) above, wherein the alkali-soluble binder has a crosslinkable group.
(8) The infrared ray shielding composition as described in any one of (1) to (7) above, wherein the fine particle of tungsten oxide containing an alkali metal is represented by formula (composition formula) (I) shown below:
MxWyOz (I)
wherein M represents an alkali metal; W represents tungsten; O represents oxygen; 0.001 < x/y < l.l; and 2.2 < ^y < 3.0.
(9) The infrared ray shielding composition as described in any one of (1) to (8) above, wherein the polymerizable compound is a polyfunctional polymerizable compound having a plurality of polymerizable groups in its molecule.
(10) The infrared ray shielding composition as described in any one of (1) to (9) above, which is used for a solder resist or an infrared ray shielding film on a rear side of a silicon substrate in a solid-state imaging device.
(11) A photosensitive layer, which is formed from the infrared ray shielding composition as described in any one of (1) to (10) above.
(12) An infrared ray shielding film, which is formed from the infrared ray shielding composition as described in any one of (1) to (10) above.
(13) A solid-state imaging device comprising a solid-state imaging device substrate having an imaging device unit formed on one surface thereof, and the infrared ray shielding film as described in (12) above provided on the other surface side of the solid-state imaging device substrate.
(14) A pattern forming method comprising, in this order, a step of forming the photosensitive layer as described in (11) above, a step of pattern-exposing the photosensitive layer to cure an exposed area, and a step of removing an unexposed area by alkali development to form a pattern.
According to the present invention, an infrared ray shielding composition having a high light shielding property in the infrared region and high light transparency in the visible region and being capable of forming an infrared ray shielding film in which the occurrence of cracking is restrained and which exhibits a high adhesion property to a substrate and high exposure sensitivity, and an infrared ray shielding film, a pattern forming method and a solid-state imaging device each using the composition can be provided.
Brief Description of Drawing
Fig. 1 is a schematic cross-sectional view showing the configuration of a camera module equipped with the solid-state imaging device according to an embodiment of the invention.
Fig. 2 is a schematic cross-sectional view showing the solid-state imaging device according to an embodiment of invention.
Fig. 3 is a plan view showing one example of a wafer-level lens array.
Fig. 4 is a cross-sectional view along the line A-A in Fig. 3.
Description of Embodiments
With respect to the description of a group (an atomic group) in the specification, when the group is indicated without specifying whether substituted or unsubstituted, the group includes both a group having no substituent and a group having a substituent. For example, "an alkyl group" includes not only an alkyl group having no substituent (an unsubstituted alkyl group) but also an alkyl group having a substituent (a substituted alkyl group).
In the specification, the term "(meth)acrylate" represents acrylate and methacrylate, the term "(meth)acryl" represents acryl and methacryl, and the term "(meth)acryloyl" represents acryloyl and methacryloyl. Also, in the specification, the term "monomeric compound" has the same meaning as the term "monomer". The monomeric compound in the invention is distinguished from an oligomer and a polymer and means a compound having a weight average molecular weight of 2,000 or less. In the specification, a polymerizable compound means a compound having a polymerizable group and may be a monomeric compound or a polymer. The polymerizable group means a group involved in a polymerization reaction.
The infrared ray shielding composition according to the invention contains a fine particle of tungsten oxide containing an alkali metal, a triazine polymerization initiator and a polymerizable compound, and may contain, if desired, a binder (preferably, an alkali-soluble binder), an infrared ray blocking agent other than the fine particle of tungsten oxide described above, a dispersing agent, an ultraviolet absorbing agent, a sensitizer, a crosslinking agent, a curing accelerator, a filler, an elastomer, a surfactant and other components.
The inventors have found that by further incorporating a triazine polymerization initiator into an infrared ray shielding composition having a high light shielding property in the infrared region and high light transparency in the visible region obtained by incorporating a fine particle of tungsten oxide containing an alkali metal, an infrared ray shielding film in which the occurrence of cracking is restrained and which exhibits a high adhesion property to a substrate and high exposure sensitivity can be formed, though the reason is not clear. The invention has been made based on this finding.
The infrared ray shielding composition according to the invention is a polymerizable composition, for example, a negative polymerizable composition and typically a negative polymerizable composition. The configuration of the composition is described below.
The description of the constituent element below is made based on the representative embodiment of the invention in some cases, but the invention should not be construed as being limited thereto. In the specification, a numerical value range represented by using the term "to" means a range which includes the numerical values described before and after the term "to" as the lower limit and the upper limit, respectively.
[1] Triazine polymerization initiator
The triazine polymerization initiator for use in the infrared ray shielding composition according to the invention is not particularly restricted as long as it has a function of initiating polymerization of the polymerizable compound by either light or heat, or both, and it can be appropriately selected depending to the purpose, but it is preferably a photopolymerization initiator. In the case of initiating the polymerization by light, a compound having photosensitivity to light from an ultraviolet region to a visible region is preferred.
In the case of initiating the polymerization by heat, an initiator capable of decomposing from 150 to 250°C is preferred.
The triazine polymerization initiator is more suitably an s-triazine derivative in which an s-triazine ring has at least one substituent, for example, a halogen atom or a halogen-substituted hydrocarbon group. The triazine polymerization initiator is preferably represented by formula (T)
Figure imgf000008_0001
ently represents a halogen-substituted hydrocarbon group, a hydrogen atom, a halogen atom, a dialkylamino group, an alkyl group, an alkoxy group or a cyano group.
( 1 2
The halogen atom for X or X or the halogen atom in the halogen-substituted hydrocarbon group includes, for example, a chlorine atom, a fluorine atom and a bromine atom, and is preferably a chlorine atom.
The halogen-substituted hydrocarbon group includes, for example, a halogen-substituted alkyl group and a halogen-substituted cycloalkyl group. The halogen-substituted alkyl group is preferably a halogen-substituted alkyl group having from 1 to 5 carbon atoms. The halogen-substituted cycloalkyl group is preferably a halogen-substituted cycloalkyl group having from 3 to 10 carbon atoms.
1 2
The alkyl group for X or X , the alkyl moiety of the dialkylamino group or the alkyl moiety of the alkoxy group is preferably an alkyl group having from 1 to 5 carbon atom, and includes, for example, a methyl group, an ethyl group, a propyl group and a butyl group.
X1 and X2 each represents more preferably a halogen-substituted hydrocarbon group, and still more preferably a halogen-substituted alkyl group. The halogen-substituted alkyl group is more preferably a monohalomethyl group, a dihalomethyl group or a trihalomethyl group, and still more preferably a trihalomethyl group.
Y1, which is not present when 1 is 0, represents an ethenylene group or an -NH- group when 1 is 1, and is preferably an ethenylene group.
B and B each independently represents an aromatic ring group which may have a substituent, and is preferably an aromatic ring group having from 5 to 15 carbon atoms. The aromatic ring group may be a heterocyclic group. Examples of the substituent include a halogen atom, a cyano group, an alkyl group, an alkoxy group, a hydroxy group, an alkyl ester group, an alkylamido group and an aryl group (preferably an aryl group having from 6 to 10 carbon atoms).
The aromatic ring constituting the aromatic ring group includes, for example, a benzene ring, a coumalin ring and a benzodioxole ring, and is preferably a benzene ring.
1 2
B is preferably a 1 ,4-phenylene group, and B is preferably a phenyl group.
1 and m each independently represents any integer selected from 0, 1 and 2.
Specific examples of the triazine polymerization initiator include
2-biphenyl-4,6-bis(rricUoromethyl)-s-triazine,
2-(3,4-dimemoxystyryl)-4,6-bis( cUoromemyl)-s-triazine,
2-( -memoxystyryl)-4,6-bis(tricUoromethyl)-s-triazine,
2-( 1 ,3-benzodioxol-5-yl)-4,6-bis(trichloromethyl)-s-triazine,
3 -chloro-5 -diemylamino-((s-triazin-2-yl)amino)-3 -phenylcoumalin,
2,4,6-tris(monochloromethyl)-s-triazine, 2,4,6-tris(dichloromethyl)-s-triazine,
2,4,6-rris(trichloromethyl)-s-triazine, 2-memyl-4,6-bis(trichloromethyl)-s-triazine,
2-n-propyl-4,6-bis(tricUoromethyl)-s-triazine,
2-(a,a,p-trocUoroethyl)-4,6-bis(trichloromethyl)-s-triazine,
2-phenyl-4,6-bis(trichloromethyl)-s-triazine,
2-(p-memoxyphenyl)-4,6-bis(tricUoromethyl)-s-triazine,
2-(3,4-epoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-cUorophenyl)-4,6-bis(trichloromethyl)-s-triazine,
2-[l-( -methoxyphenyl)-2,4-butadienyl]-4,6-bis(tricWoromethyl)-s-triazm^
2-styryl-4,6-bis(trichloromethyl)-s-triazine,
2-( -isopropyloxystyryl)-4,6-bis(tricUoromethyl)-s-triazine,
2-( -tolyl)-4,6-bis(trichloromethyl)-s-triazine,
2-(4-methoxynaph1hyl)-4,6-bis( cUoromethyl)-s-triazine,
2-phenyltWo-4,6-bis(trichloroniethyl)-s-triazine, 2-benzyltMo-4,6-bis(1ricWoromethyl)-s-triazine, 2,4,6-tris(dibromomethyl)-s-triazine, 2,4,6-lris(tribromomethyl)-s-triazine,
2-methyl-4,6-bis(tribromomethyl)-s-triazine, and 2-methoxy-4,6-bis(tribromomethyl)-s-triazine. Of the compounds, 2-biphenyl-4,6-bis(trichloromethyl)-s-triazine,
2-(3,4-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine,
2-( -memoxystyryl)-4,6-bis(tricUoromethyl)-s-triazine,
2- (l ,3-benzodioxol-5-yl)-4,6-bis(trichloromethyl)-s-triazine or
3 - cWoro-5-diemylammo-((s-triazin-2-yl)amino)-3 -phenylcoumalin is preferred,
2-biphenyl-4,6-bis(trichloromethyl)-s-triazine,
2-(3,4-dimemoxystyiyl)-4,6-bis(trichloromethyl)-s-triazine or
2-(p-methoxys1yiyl)-4,6-bis(tricUoromethyl)-s-triazine is more preferred,
2-biphenyl-4,6-bis(tricWoromemyl)-s-triazine or
2-(3,4-dimemoxys1yryl)-4,6-bis(tricUoromethyl)-s-triazine is still more preferred, and
2-biphenyl-4,6-bis(trichloromethyl)-s-triazine is particularly preferred.
Specific examples of the triazine polymerization initiator for use in the infrared ray shielding composition according to the invention are set forth below, but the invention should not be construed as being limited thereto.
Figure imgf000011_0001
The triazine polymerization initiators may be used individually or in combination of two or more thereof.
The content of the triazine polymerization initiator is preferably from 0.01 to 30% by weight, more preferably from 0.1 to 20% by weight, particularly preferably from 0.1 to 15% by weight, based on the total solid content of the infrared ray shielding composition according to the invention.
(Combination polymerization initiator)
The infrared ray shielding composition according to the invention may contain a polymerization initiator (hereinafter, also simply referred to as a "combination polymerization initiator") other than the triazine polymerization initiator described above.
As the combination polymerization initiator according to the invention, compounds known as polymerization initiators described below can be employed.
The combination polymerization initiator is not particularly restricted as long as it has an ability of initiating polymerization of the polymerizable compound described above and may be appropriately selected from known polymerization initiators. For example, those having radiation sensitivity to light in the region from ultraviolet to visible are preferred. The initiator may also be an activator capable of causing a certain action with a photoexcited sensitizer to generate an active radical or an initiator capable of initiating cationic polymerization depending on the kind of the monomer.
Further, the combination polymerization initiator preferably contains at least one kind of compound having a molecular extinction coefficient of at least about 50 in the range from about 300 to about 800 nm (more preferably from 330 to 500 nm).
Examples of the combination polymerization initiator include a halogenated hydrocarbon derivative (for example, a compound having an oxadiazole skeleton), an acylphosphine compound, for example, an acylphosphine oxide, a hexaarylbiimidazole, an oxime compound, for example, an oxime derivative, an organic peroxide, a thio compound, a ketone compound, an aromatic onium salt, a ketoxime ether, an aminoacetophenone compound and a hydroxyacetophenone.
The compound having an oxadiazole skeleton includes, for example, compounds described in U. S . Patent 4,212,976. Specific examples thereof include
2-trichloromethyl-5-phenyl- 1 ,3,4-oxadiazole, 2-trichloromethyl-5-(4-chlorophenyl)- 1 ,3,4-oxadiazole, 2-trichloromethyl-5-(l -naphthyl)- 1 ,3,4-oxadiazole,
2-trichloromethyl-5-(2-naphthyl)- 1 ,3,4-oxadiazole, 2-tf bromomethyl-5-phenyl- 1 ,3,4-oxadiazole,
2-tribromomethyl-5-(2-naphthyl)- 1 ,3,4-oxadiazole, 2-trichloromethyl-5-styryl- 1 ,3 ,4-oxadiazole,
2-trichloromethyl-5-(4-chlorosryryl)-l,3,4-oxadiazole,
2-trichloromethyl-5 -(4-methoxystyryl)- 1 ,3 ,4-oxadiazole,
2-trichloromethyl-5-(l -naphthyl)- 1 ,3,4-oxadiazole,
2-trichloromethyl-5-(4-n-buthoxystyryl)- 1 ,3 ,4-oxadiazole,
2- tribromomethyl-5-styryl- 1 ,3,4-oxadiazole).
Examples of the combination polymerization initiator other than those described above include an acridine derivative (e.g., 9-phenylacridine, l,7-bis(9,9'-acridinyl)heptane),
N-phenylglycine, a polyhalogen compound (e.g., carbon tetrabromide, phenyl tribromomethyl sulfone or phenyl trichloromethyl ketone), a coumarin (e.g.,
3 -(2-benzoflu,oyl)-7-diemylammocoumarin, 3 -(2-benzofuroyl)-7-( 1 -pyrrolidinyl)coumarin,
3- benzoyl-7-diethylaminocoumarin, 3-(2-memoxybenzoyl)-7-diethylaminocoumarin,
3 -(4-dimemylaminobenzoyl)-7-diemylaminocoumarin, 3 ,3 ' -carbonylbis(5 ,7-di-n-propoxycoumarin), 3,3' -carbonylbis(7-diethylaminocoumarin), 3 -benzoy 1-7-methoxycoumarin,
3-(2-furoyl)-7-diemylarninocoumarin, 3-(4-diethylammocinnamoyl)-7-diethylaminocoumarin, 7-methoxy-3 -(3 -pyridylcarbonyl)coumarin, 3 -benzoy 1-5,7-dipropoxycoumarin,
7-benzotriazol-2-ylcoumarin, coumarin compounds described, for example, in JP-A-5-19475, JP-A-7-271028, JP-A-2002-363206, JP-A-2002-363207, JP-A-2002-363208 and
JP-A-2002-363209), an acylphosphine oxide (e.g., bis(2,4,6-tiimemylbenzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphenylphosphine oxide or Lucirin TPO), a metallocene (e.g.,
bis(n5-2,4-cyclopentadien- 1 -yl)-bis(2,6-difluoro-3-( 1 H-pyrrol- 1 -yl)phenyl)titanium or
η5-cyclopentadienyl-η6-cumenyl-iron(l+)-hexafluorophosphate (1-)), and compounds described, for example, in JP-A-53-133428, JP-B-57-1819, JP-B-57-6096 and U.S. Patent 3,615,455.
Examples of the ketone compound include benzophenone, 2-methylbenzophenone,
3- methylbenzophenone, 4-methylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone,
4- chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone,
2-ethoxycarbonylbenzophenone, benzophenone tetracarboxylic acid or a tetramethyl ester thereof, a 4,4'-bis(dialkylamino)benzophenone (e.g., 4,4'-bis(dimethylamino)benzophenone,
4,4' -bis(dicyclohexylamino)benzophenone, 4,4 ' -bis(diethylamino)benzophenone,
4,4'-bis(dihydroxyethylamino)benzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 4,4'-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylaminoacetophenone, benzyl, anthraquinone, 2-tert-butylanthraquinone, 2-methylanthraquinone, phenanthraquinone, xanthone, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, fluorenone,
2-benzyl-2-dimethylamino- 1 -(4-morpholinophenyl)- 1 -butanone,
2-methyl-l-[4-(methylthio)phenyl]-2-mo holino-l-propanone,
2-hydroxy-2-methyl-[4-(l-methylvinyl)phenyl]propanol oligomer, benzoin, a benzoin ether (e.g., benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin phenyl ether, benzyl dimethyl ketal), acridone, chloroacridone, N-methylacridone, N-butylacridone and N-butyl-chloroacridone.
A hydroxyacetophenone compound, an aminoacetophenone compound and an acylphosphine compound may also be suitably used as the combination polymerization initiator. More specifically, for example, an aminoacetophenone initiator described in JP-A- 10-291969 and an acylphosphine oxide initiator described in Japanese Patent 4225898 may be used.
As the hydroxyacetophenone initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959 and IRGACURE-127 (produced by BASF) may be used. As the aminoacetophenone initiator, commercially available products of IRGACURE-907, IRGACURE-369 and IRGACURE-379 (produced by BASF) may be used. As the aminoacetophenone initiator, compounds in which the absorption wavelength matches a light source having a long wavelength, for example, 365 nm or 405 nm described in JP-A-2009-191179 may be also used. As the acylphosphine initiator, commercially available products of IRGACURE-819 and DAROCUR-TPO (produced by BASF) may be used.
An oxime compound is also suitably used as the combination polymerization initiator. Specific examples of the oxime initiator used include compounds described in JP-A-2001 -233842, compounds describe in JP-A-2000-80068 and compounds described in JP-A-2006-342166.
Examples of the oxime compound, for example, an oxime derivative, which is suitably used as the combination polymerization initiator in the invention, include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3 -one, 2-acetoxyimino- 1 -phenylpropan- 1 -one,
2-benzoyloxyimino- 1 -phenylpropan- 1 -one, 3 -(4-toluenesulfonyloxy)iminobutan-2-one and
2-ethoxycarbonyloxyimino- 1 -phenylpropan- 1 -one.
Examples of the oxime ester compound include compounds described in J. C. S. Perkin II, pp. 1653-1660 (1979), J. C. S. Perkin II, pp. 156-162 (1979), Journal of Photopolvmer Science and Technology, pp. 202-232 (1995), Journal of Applied Polymer Science, pp. 725-731 (2012) and JP-A-2000-66385, and compounds described in JP-A-2000-80068, JP-T-2004-534797 and JP-A-2006-342166.
As a commercially available product, IRGACURE-OXE01 (produced by BASF), IRGACURE-OXE02 (produced by BASF) and TR-PBG-304 (produced by Changzhou Tronly New Electric Materials Co., Ltd.) may also be suitably used.
As the oxime ester compound other than those described above, for example, compounds described in JP-T-2009-519904 where oxime is connected to N-position of carbazole, compounds described in U.S. Patent 7,626,957 where a hetero substituent is introduced into a benzophenone moiety, compounds described in JP-A-2010-15025 and U.S. Patent Application Publication No. 2009-292039 where a nitro group is introduced into a dye moiety, ketoxime compounds described in WO 2009/131189, compounds containing a triazine skeleton and an oxime skeleton in the same molecule described in U.S. Patent 7,556,910, and compounds having an absorption maximum at 405 nm and exhibiting good sensitivity to a g-ray light source described in JP-A-2009-221114 may be also used.
Furthermore, cyclic oxime compounds described in JP-A-2007-231000 and JP-A-2007-322744 may be also suitably used. Of the cyclic oxime compounds, cyclic oxime compounds fused to a carbazole dye described in JP-A-2010-32985 and JP-A-2010-185072 are preferred from the standpoint of high light absorbing property and high sensitivity.
Also, compounds having an unsaturated bond at a specific site thereof described in JP-A-2009-242469 can be suitably used because they can achieve high sensitivity by regenerating an active radical from a polymerization inactive radical.
In addition, oxime compound having a specific substituent described in JP-A-2007-269779 and the oxime compound having a thioaryl group described in JP-A-2009-191061 are exemplified.
Specific examples (PIox-1) to (PIox-13) of the oxime compound suitably used are set forth below, but the invention should not be construed as being limited thereto.
Figure imgf000015_0001
The combination polymerization initiator which may be used in the infrared ray shielding composition according to the invention is preferably a compound selected from the group consisting of a benzyldimethylketal compound, an a-hydroxyketone compound, an a-aminioketone compound, an acylphosphine compound, a phosphinoxide compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, an onium compound, a benzothiazole compound, a benzophenone compound, an acetophenone compound or a derivative thereof, cyclopentadiene-benzene-iron complex or a salt thereof, a halomethyloxadiazole compound and a 3-aryl-substituted coumarin compound.
It is more preferably a compound selected from the group consisting of an a-aminioketone compound, an acylphosphine compound, a phosphinoxide compound, an oxime compound, a triarylimidazole dimer, an onium compound, a benzophenone compound and an acetophenone compound, and most preferably a compound selected from the group consisting of an α-aminioketone compound, an oxime compound, a triarylimidazole dimer and a benzophenone compound.
The content (total content, in case of using two or more) of the combination polymerization initiator contained in the infrared ray shielding composition according to the invention is preferably from 0.001 to 10% by weight, more preferably from 0.01 to 5% by weight, based on the total solid content of the infrared ray shielding composition.
[2] Polymerizable compound
The infrared ray shielding composition according to the invention contains a polymerizable compound. The polymerizable compound used may be any compound as long as it is a compound having a functional group capable of undergoing a reaction with at least one of an acid, a radical and heat (in the specification, such a functional group is sometimes referred to as a "polymerizable group") in its molecule, and is preferably a polyfunctional polymerizable compound having a plurality of polymerizable groups in its molecule.
Examples of the polymerizable compound having a polymerizable functional group capable of reacting with at least one of an acid, a radical and heat include an ethylenically unsaturated group-containing compound having an ethylenically unsaturated group, for example, an unsaturated ester functional group, an unsaturated amido group, a vinyl ether group or an allyl group, a methylol compound, a bismaleimide compound, a benzocyclobutene compound, a bisallylnadiimide compound and a benzoxazine compound.
The polymerizable compound which can be preferably used in the invention includes an ordinal radical polymerizable compound and compounds widely known as the compound having an ethylenically unsaturated double bond in the field of art can be used without any particular restriction.
The compound has a chemical form, for example, of a monomer, a prepolymer (specifically, a dimer, a trimer or an oligomer), or a mixture thereof or a copolymer thereof.
Examples of the monomer and copolymer thereof include an unsaturated carboxylic acid (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid or maleic acid), its ester and amide, and copolymer thereof. Preferably, an unsaturated carboxylic acid ester, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound and an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound are used.
Particularly, the ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound can exhibit high hydrophobicity in the exposed area and is preferred because a pattern having a desired profile is easily formed by alkali development and also a pattern having high durability is obtained (in particular, when higher durability is required of the solder resist, for example, in the case where the wiring density of the metal wiring covered with the solder resist is high, the effects described above are significant).
In addition, for example, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent, for example, a hydroxy group, an amino group or a mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and a dehydration condensation reaction product of the unsaturated carboxylic acid ester or amide with a monofunctional or polyfunctional carboxylic acid are also suitably used.
An addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent, for example, an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, and a substitution reaction product of an unsaturated carboxylic acid ester or amide having a releasable substituent, for example, a halogen group or a tosyloxy group with a monofunctional or polyfunctional alcohol, amine or thiol are also suitable. As another example, a compound in which the unsaturated carboxyl acid described above is replaced, for example, with an unsaturated phosphonic acid, styrene or vinyl ether may also be used.
The unsaturated carboxylic acid ester is preferably a methacrylic acid ester and examples thereof include tetramethylene glycol dimethacrylate, Methylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis[p-(3-methacryloxy-2-hydroxypropoxy)phenyl]dimethylmethane, bis-[p-(methacryloxyethoxy)phenyl]dimethylmethane and their EO-modified or PO-modified products.
The unsaturated carboxylic acid ester is also preferably an itaconic acid ester and examples thereof include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate and sorbitol tetraitaconate. Examples of the crotonic acid ester include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate and sorbitol tetradicrotonate. Examples of the isocrotonic acid ester include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate and sorbitol tetraisocrotonate. Examples of the maleic acid ester include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate and sorbitol tetramaleate.
Specific examples of the ester monomer of an aliphatic polyhydric alcohol compound with an unsaturated carboxylic acid include, as the (meth)acrylic acid ester, ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri(acryloyloxypropyl)ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, tricyclodecanedimethanol diacrylate, tricyclodecanedimethanol dimethacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri(acryloyloxyethyl) isocyanurate, polyester acrylate oligomer and EO-modified or PO-modified products of these compounds.
Other esters, for example, aliphatic alcohol esters described in JP-B-51-47334 (the term "JP-B" as used herein means an "examined Japanese patent publication") and JP-A-57- 196231, those having an aromatic skeleton described in JP-A-59-5240, JP-A-59-5241 and JP-A-2-226149 and those having an amino group described in JP-A-1-165613 are also suitably used. The ester monomers described above may also be used as a mixture.
Specific examples of the amide monomer of an aliphatic polyvalent amine compound with an unsaturated carboxylic acid include methylene bisacrylamide, methylene bismethacrylamide, 1,6-hexamethylene bisacrylamide, 1,6-hexamethylene bismethacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide and xylylene bismethacrylamide. Other preferred examples of the amide monomer include those having a cyclohexylene structure described in JP-B-54-21726.
A urethane-based addition-polymerizable compound produced by an addition reaction of an isocyanate with a hydroxy group is also suitable, and specific examples thereof include a vinyl urethane compound having two or more polymerizable vinyl groups per molecule obtained by adding a hydroxy group-containing vinyl monomer represented by formula (E) shown below to a polyisocyanate compound having two or more isocyanate groups per molecule described in JP-B-48-41708.
CH2=C(R4)COOCH2CH(R5)OH (E)
(wherein R4 and R5 each independently represents H or CH3.)
Further, urethane acrylates described in JP-A-51-37193, JP-B-2-32293 and JP-B-2-16765 and urethane compounds having an ethylene oxide skeleton described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417 and JP-B-62-39418 are also suitable. In addition, when addition-polymerizable compounds having an amino structure or sulfide structure in the molecule described in JP-A-63-277653, JP-A-63 -260909 and JP-A-1 -105238 are used, an infrared ray shielding composition having very excellent in the photosensitive speed can be obtained.
Other examples include polyfunctional acrylate or methacrylate, for example, polyester acrylates described in JP-A-48-64183, JP-B-49-43191 and JP-B-52-30490, and epoxy acrylates obtained by reacting an epoxy resin with (meth)acrylic acid. Other examples also include specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337 and JP-B-1-40336, and vinylphosphonic acid compounds described in JP-A-2-25493. In some cases, a perfluoroalkyl group-containing structure described in JP-A-61-22048 is suitably used. Furthermore, photocurable monomers and oligomers described in Journal of The Adhesion Society of Japan. Vol. 20, No. 7, pp. 300-308 (1984) may also be used.
In the invention, when a radical polymerizable compound is added, from the standpoint of curing sensitivity, a polyfunctional polymerizable compound containing two or more ethylenically unsaturated bonds is preferably used, and it is more preferred to contain three or more ethylenically unsaturated bonds. Among them, a compound containing two or more (meth)acrylic acid ester structures is preferred, a compound containing three or more (meth)acrylic acid ester structures is more preferred, and a compound containing four or more (meth)acrylic acid ester structures is most preferred.
Furthermore, from the standpoint of curing sensitivity and development property of the unexposed area, a compound containing an EO-modified product is preferred, and from the standpoint of curing sensitivity and strength of the exposed area, a compound containing a urethane bond is also preferably used. In addition, from the standpoint of development property at the pattern formation, a compound having an acid group is preferably used.
From the standpoint described above, preferred examples of the polymerizable compound for use in the invention include bisphenol A diacrylate, EO-modified bisphenol A diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri(acryloyloxypropyl)ether, trimethylolethane triacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythntol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaaciylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaaciylate, tri(acryloyloxyethyl)isocyanurate, EO-modified pentaerythritol tetraacrylate, EO-modified dipentaerythritol hexaaciylate and tricyclodecanedimethanol diacrylate. Also, as commercially available products, U ETHANE OLIGOMER UAS-10, UAB-140 (produced by Sanyo Kokusaku Pulp Co., Ltd.), DPHA-40H (produced by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600 and AI-600 (produced by Kyoeisha Chemical Co., Ltd.) and A-DCP (produced by Shin-Nakamura Chemical Co., Ltd.) are preferred.
Among them, EO-modified bisphenol A diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tri(acryloyloxyethyl)isocyanurate, EO-modified pentaerythritol tetraacrylate and EO-modified dipentaerythritol hexaacrylate are more preferred, and as the commercially available products, DPHA-40H (produced by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600 and AI-600 (produced by Kyoeisha Chemical Co., Ltd.) and A-DCP (produced by Shin-Nakamura Chemical Co., Ltd.) are more preferred.
An ethylenically unsaturated compound having an acid group is also suitable, and examples of the commercially available product thereof include TO-756 which is a carboxyl group-containing Afunctional aery late and TO- 1382 which is a carboxyl group-containing pentafunctional acrylate, produced by Toagosei Co., Ltd.
In addition, examples of the highly heat resistant polymerizable compound include benzocyclobutene (BCB), bisallylnadiimide (BAND, benzoxazine, melamine and its analogues.
Also, two or more kinds of the polymerizable compounds may be used.
The content of the polymerizable compound is preferably from 3 to 80% by weight, more preferably from 5 to 50% by weight, based on the total solid content of the infrared ray shielding composition according to the invention.
The polymerizable compound may be the same as or different from a binder (preferably, an alkali-soluble binder).
More specifically, when the polymerizable compound is a polymer, the polymerizable compound may be the same as the alkali-soluble binder described in detail hereinafter (that is, the polymerizable compound may be the same component as the alkali-soluble binder). In this embodiment, the content of the polymerizable compound is preferably from 3 to 80% by weight, more preferably from 5 to 60% by weight, based on the total solid content of the infrared ray shielding composition according to the invention.
[3] Fine particle of tungsten oxide containing alkali metal The infrared ray shielding composition according to the invention contains a fine particle of tungsten oxide containing an alkali metal.
The fine particle of tungsten oxide containing an alkali metal is an infrared ray blocking agent having high absorption for infrared ray (light having a wavelength approximately from 800 to 1,200 nm) (that is, the light shielding property (light blocking property) for infrared ray is high) and low absorption for visible light. Thus, the infrared ray shielding composition according to the invention can form an infrared ray shielding film having a high light shielding property in the infrared region and high light transparency in the visible region by containing the fine particle of tungsten oxide containing an alkali metal.
Also, the fine particle of tungsten oxide containing an alkali metal exhibits also small absorption for light shorter than the visible region, which is employed in exposure with a high-pressure mercury lamp, KrF, ArF or the like used in the image formation. Therefore, the excellent pattern is obtained by further incorporating an alkali-soluble binder into the infrared ray shielding composition containing the fine particle of tungsten oxide containing an alkali metal according to the invention.
The fine particle of tungsten oxide containing an alkali metal is preferably represented by formula (composition formula) (I) shown below.
MxWyOz (I)
In formula (I), M represents an alkali metal; W represents tungsten; O represents oxygen; 0.001 < x/y < 1.1; and 2.2 < z/y < 3.0.
The alkali metal represented by M may be one kind or two or more kinds.
The alkali metal represented by M is preferably Rb or Cs, and more preferably Cs.
When x/y is 0.001 or more, an infrared ray can be sufficiently blocked, and when it is 1.1 or less, generation of an impurity phase in the fine particle of tungsten oxide containing an alkali metal can be more steadily avoided.
When z y is 2.2 or more, a chemical stability as the material can be more improved, and when it is 3.0 or less, an infrared ray can be sufficiently blocked.
Specific examples of the fine particle of tungsten oxide containing an alkali metal represented by formula (I) include Cs033WO3, Rb0.33WO3 and Ko.33W03. The fine particle of tungsten oxide containing an alkali metal is preferably CS033WO3 or Rb033WO3, and more preferably CS033WO3.
The average particle size of the fine particle of tungsten oxide containing an alkali metal is preferably 800 nm or less, more preferably 400 nm or less, and still more preferably 200 nm or less. When the average particle size is in the range described above, the fine particle of tungsten oxide containing an alkali metal can hardly block visible light by light scattering so that light transparency in the visible light region can be more ensured. From the standpoint of avoiding light scattering, the average particle size is preferably smaller, but for reasons of easy handling property or the like at the production, the average particle size of the fine particle of tungsten oxide containing an alkali metal is preferably 1 run or more.
The content of the fine particle of tungsten oxide containing an alkali metal is preferably from 3 to 20% by weight, more preferably from 5 to 10% by weight, based on the total solid content of the infrared ray shielding composition according to the invention.
Also, two or more kinds of the fine particles of tungsten oxide containing an alkali metal may be used.
The fine particle of tungsten oxide containing an alkali metal is available as a commercial product, and it can be obtained by a method of heat-treating a tungsten compound containing an alkali metal in an inert gas atmosphere or a reducing gas atmosphere (see, Japanese Patent No. 4,096,205).
Also, a dispersion of the fine particle of tungsten oxide containing an alkali metal, for example, YMF-02 produced by Sumitomo Metal Mining Co., Ltd. is available.
[4] Binder
The infrared ray shielding composition according to the invention may contain a binder.
The binder can be appropriately selected according to the purpose, and examples thereof include a (meth)acrylic resin, a urethane resin, a polyvinyl alcohol, a polyvinyl butyral, a polyvinyl formal, a polyamide and a polyester, and preferably includes a (meth)acrylic resin and a urethane resin. For instance, examples of the binder having no alkali solubility include a (meth)acrylic resin, a urethane resin, a polyvinyl alcohol, a polyvinyl butyral, a polyvinyl formal, a polyamide and a polyester each having no alkali solubility because of having no acid group and include a polymer obtained by polymerization of a polymerizable compound having no acid group described below.
The binder is preferably an alkali-soluble binder (alkali-soluble resin). By containing the alkali-soluble binder, when an infrared ray shielding film obtained from the infrared ray shielding composition is exposed to form a pattern, the unexposed area can be removed with an alkali developer so that an excellent pattern can be formed by alkali development.
The alkali-soluble binder is not particularly restricted as long as it is soluble in alkali, and can be appropriately selected according to the purpose. Examples thereof include a (meth)acrylic resin, a urethane resin, a polyvinyl alcohol, a polyvinyl butyral, a polyvinyl formal, a polyamide and a polyester, and preferably includes a (meth)acrylic resin and a urethane resin.
The alkali-soluble binder preferably has an acid group. The acid group includes, for example, a carboxylic acid group, a sulfonic acid group, a phosphonic acid group, a phosphoric acid group and a sulfonamido group, and is preferably a carboxylic acid group from the standpoint of availability of raw materials.
The alkali-soluble binder having an acid group is not particularly restricted and is preferably a polymer obtained by using an acid group-containing polymerizable compound as a monomer component, and from the standpoint of adjustment of acid value, more preferably a copolymer obtained by copolymerizing a polymerizable compound having an acid group and a polymerizable compound having no acid group.
The polymerizable compound having an acid group is not particularly restricted and may be appropriately selected according to the purpose, and examples thereof include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid and p-carboxylstyrene. Among them, acrylic acid, methacrylic acid or p-carboxylstyrene is preferred. The polymerizable compounds having an acid group may be used individually or in combination of two or more thereof.
The polymerizable compound having no acid group is not particularly restricted and suitable examples thereof include a (meth)acrylic acid ester (for example, an alkyl ester, an aryl ester or an aralkyl ester).
The alkyl group in the alkyl ester moiety of the (meth)acrylic acid ester may be straight-chain or branched and is preferably an alkyl group having from 1 to 10 carbon atoms, and more preferably an alkyl group having from 1 to 6 carbon atoms.
The aryl group in the aryl ester moiety of the (meth)acrylic acid ester is preferably an aryl group having from 6 to 14 carbon atoms, and more preferably an aryl group having from 6 to 10 carbon atoms.
The aralkyl group in the aralkyl ester moiety of the (meth)acrylic acid ester is preferably an aralkyl group having from 7 to 20 carbon atoms, and more preferably an aralkyl group having from 7 to 12 carbon atoms.
The molar ratio between the monomer corresponding to the polymerizable compound having an acid group and the monomer corresponding to the polymerizable compound having no acid group is ordinarily from 1 : 99 to 99 : 1, preferably from 30 : 70 to 99 : 1, and more preferably
Figure imgf000023_0001
The content of the acid group in the alkali-soluble binder is not particularly restricted and is preferably from 0.5 to 4.0 meq/g, and more preferably from 0.5 to 3.0 meq/g. When the content of the acid group is 0.5 meq/g or more, the alkali development property is sufficiently obtained and an excellent pattern can be more steadily obtained. When the content of the acid group is 4.0 meq/g or less, the risk of impairing the strength of the infrared ray shielding film in which the pattern is formed can be surely avoided.
The alkali-soluble binder preferably further has a crosslinkable group and by the introduction of crosslinkable group, both curing property of the exposed area and alkali development property of the unexposed area can be particularly improved. The introduction of crosslinkable group is also preferred because a pattern having high durability is obtained (in particular, this effect is significant when higher durability is required of the solder resist, for example, in the case where the wiring density of metal wiring covered with the solder resist is high). The crosslinkable group is a group capable of crosslinking the binder polymer in the course of a polymerization reaction occurring in the photosensitive layer when the photosensitive layer obtained from the infrared ray shielding composition (polymerizable composition) is exposed or heated. The crosslinkable group is not particularly restricted as long as it is a group having such a function, and examples thereof include as a functional group capable of undergoing an addition polymerization reaction, an ethylenically unsaturated bond group, an amino group and an epoxy group. The crosslinking group may also be a functional group capable of forming a radical upon irradiation with light, and examples thereof include a thiol group and a halogen group. Among them, an ethylenically unsaturated bond group is preferred. The ethylenically unsaturated bond group is preferably a styryl group, a (meth)acryloyl group or an allyl group and from the standpoint of satisfying both stability of the crosslinkable group before exposure and strength of the infrared ray shielding film in which the pattern is formed, more preferably a (meth)acryloyl group.
In the alkali-soluble binder, for example, a free radical (a polymerization initiating radical or a propagating radical in the course of polymerization of the polymerizable compound) is added to the crosslinkable functional group to cause addition polymerization between polymers directly or through a polymerization chain of the polymerizable compound and as a result, crosslinking is formed between the polymer molecules to effect curing. Alternatively, an atom (for example, a hydrogen atom on a carbon atom adjacent to the functional crosslinkable group) in the polymer is withdrawn by a free radical to produce a polymer radical, and polymer radicals combine with each other to form crosslinking between the polymer molecules, whereby curing is effected.
The content of the crosslinkable group in the alkali-soluble binder is not particularly restricted and is preferably from 0.5 to 3.0 meq/g, more preferably from 1.0 to 3.0 meq/g, and particularly preferably from 1.5 to 2.8 meq/g. When the content of the crosslinkable group is 0.5 meq/g or more, an amount of curing reaction is sufficient so that the high sensitivity can be achieved, and when it is 3.0 meq/g or less, the infrared ray shielding composition can have high preservation stability. The content (meq/g) can be measured, for example, by iodine number titration.
The alkali-soluble binder having a crosslinkable group is described in detail in JP-A-2003-262958 and compounds described therein can also be used in the invention.
The alkali-soluble binder having a crosslinkable group is preferably an alkali-soluble binder having an acid group and a crosslinkable group and the representative examples thereof are described below.
(1) A urethane-modified polymerizable double bond-containing acrylic resin obtained by a reaction of a compound in which an isocyanate group and a hydroxy group are previously reacted to leave one unreacted isocyanate group and which has at least one (meth)acryloyl group with an acrylic resin containing a carboxyl group.
(2) An unsaturated group-containing acrylic resin obtained by reacting an acrylic resin containing a carboxyl group with a compound having both an epoxy group and a polymerizable double bond in its molecule.
(3) A polymerizable double bond-containing acrylic resin obtained by reacting an acrylic resin containing a hydroxy group with a dibasic acid anhydride having a polymerizable double bond.
Of the resins described above, the resins of (1) and (2) are preferred.
Also, examples of the alkali-soluble binder having an acid group and a crosslinkable group include a polymer compound having an acidic group and an ethylenically unsaturated bond in its side chain and having a bisphenol A-type skeleton or a bisphenol F-type skeleton and a novolac resin and resol resin each having an acidic group and an ethylenically unsaturated bond. These resins can be obtained by a method described in paragraphs [0008] to [0027] of JP-A-11-240930.
As described above, the alkali-soluble binder is preferably a (meth)acrylic resin or a urethane resin. The "(meth)acrylic resin" is preferably a copolymer having, as a polymerization component, a (meth)acrylic acid derivative, for example, (meth)acrylic acid, a (meth)acrylic acid ester (e.g., an alkyl ester, an aryl ester or an aralkyl ester), (meth)acrylamide and a (meth)acrylamide derivative. The "urethane resin" is preferably a polymer produced by a condensation reaction between a compound having two or more isocyanate groups and a compound having two or more hydroxy groups.
Suitable examples of the (meth)acrylic resin include a copolymer containing a repeating unit having an acid group. Suitable examples of the acid group include those described above. The repeating unit having an acid group is preferably a repeating unit derived from (meth)acrylic acid or a repeating unit represented by formula (I) shown below.
Figure imgf000026_0001
1 2
In formula (I), R represents a hydrogen atom or a methyl group; R represents a single bond or an (n+l)-valent connecting group; A represents an oxygen atom or -NR3-; R3 represents a hydrogen atom or a monovalent hydrocarbon group having from 1 to 10 carbon atoms; and n represents an integer from 1 to 5.
In formula (I), the connecting group represented by R2 is preferably composed of one or more kinds of atoms selected from the group consisting of a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom and a halogen atom, and the number of atoms constituting the connecting group represented by R2 is preferably from 1 to 80. Specific examples of the connecting group include an alkylene group and an arylene group, and the connecting group may have a structure where a plurality of these divalent groups are connected by any of an amido bond, an ether bond, a urethane bond, a urea bond and an ester bond. R2 is preferably a single bond, an alkylene group or a structure where a plurality of alkylene groups are connected by at least any of an amido bond, an ether bond, a urethane bond, a urea bond and ester bond.
The carbon number of the alkylene group is preferably from 1 to 5, and more preferably from 1 to 3.
The carbon number of the arylene group is preferably from 6 to 14, and more preferably from 6 to 10.
The alkylene group and arylene group may further have a substituent and the substituent includes a monovalent nonmetallic atomic group excluding a hydrogen atom. Examples thereof include a halogen atom (-F, -Br, -CI or -I), a hydroxy group, a cyano group, an alkoxy group, an aryloxy group, a mercapto group, an alkylthio group, an arylthio group, an alkylcarbonyl group, an arylcarbonyl group, a carboxyl group and its conjugate base group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an aryl group, an alkenyl group and an alkynyl group.
The hydrocarbon group represented by R3 preferably has a carbon number from 1 to 10, more preferably from 1 to 5, and still more preferably from 1 to 3.
R is most preferably a hydrogen atom or a methyl group.
n is preferably 1 to 3, more preferably 1 or 2, and most preferably 1.
The ratio (% by mole) of the acid group-containing repeating unit based on the total repeating unit of the (meth)acrylic resin is preferably from 10 to 90% from the standpoint of development property. In consideration of satisfying both the development property and the strength of the infrared ray shielding film in which the pattern is formed, it is more preferably from 50 to 85%, and particularly preferably from 60 to 80%.
As described above, the (meth)acrylic resin preferably further has a crosslinkable group, and the specific examples and content of the crosslinkable group are the same as those described above.
The (meth)acrylic polymer for use in the invention may contain, in addition to the polymerization unit having an acid group and the polymerization unit having a crosslinkable group, a polymerization unit composed of an alkyl or aralkyl (meth)acrylate, a polymerization unit composed of (meth)acrylamide or its derivative, a polymerization unit composed of an a-hydroxymethyl acrylate or a polymerization unit composed of a styrene derivative. The alkyl group in the alkyl (meth)acrylate is preferably an alkyl group having from 1 to 5 carbon atoms or an alkyl group containing the substituent described above and having from 2 to 8 carbon atoms, and more preferably a methyl group. Examples of the aralkyl (meth)acrylate include benzyl (meth)acrylate. Examples of the (meth)acrylamide derivative include N-isopropylacrylamide, N-phenylmethacrylamide, N-(4-methoxycarbonylphenyl)methacrylamide, N,N-dimethylacrylamide and mo holinoacrylamide. Examples of the a-hydroxymethyl acrylate include ethyl a-hydroxymethyl acrylate and cyclohexyl α-hydroxymethyl acrylate. Examples of the styrene derivative include styrene and 4-tert-butylstyrene.
The "urethane resin" is preferably a urethane resin having, as the basic skeleton, a structural unit represented by a reaction product between at least one diisocyanate compound represented by formula (1) shown below and at least one diol compound represented by formula (2) shown below.
OCN-X-NCO (1)
HO-L'-OH (2)
In formulae (1) and (2), X and L1 each independently represent a divalent organic residue.
At least one diol compound represented by formula (2) preferably has an acid group. Thus, an alkali-soluble urethane resin having the acid group introduced can be suitably produced as a reaction product of the diisocyanate compound and the diol compound. According to the method, an alkali-soluble urethane resin can be more easily produced than in the case of substituting and introducing an acid group in the desired side chain after the reaction and production of a urethane resin.
At least one compound of the diisocyanate compound represented by formula (1) and the diol compound represented by formula (2) preferably has a crosslinkable group. Examples of the crosslinkable group include those described above. Thus, an alkali-soluble urethane resin having the crosslinkable group introduced can be suitably produced as a reaction product of the diisocyanate compound and the diol compound. According to the method, a crosslinkable group-containing urethane resin can be more easily produced than in the case of substituting and introducing a crosslinkable group in the desired side chain after the reaction and production of a urethane resin.
(1) Diisocyanate Compound
In formula (1), X is preferably a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group or a group formed by combination thereof, and a number of carbon atoms included is preferably from 1 to 20, and more preferably from 1 to 15. The divalent aliphatic or aromatic hydrocarbon group may further has a substituent incapable of reacting with an isocyanate group.
Specific examples of the diisocyanate compound represented by formula (1) include an aromatic diisocyanate compound, for example, 2,4-tolylene diisocyanate, 2,4-tolylene diisocyanate dimer, 2,6-tolylene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate,
4,4'-diphenylmethane diisocyanate, 1 ,5-naphthylene diisocyanate or
3,3 '-dimethylbiphenyl-4,4' -diisocyanate; an aliphatic diisocyanate compound, for example, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate or dimer acid diisocyanate; an alicyclic diisocyanate compound, for example, isophorone diisocyanate, 4,4'-methylenebis(cyclohexylisocyanate), methylcyclohexane-2,4 (or 2,6)-diisocyanate or l,3-(isocyanatomethyl)cyclohexane; and a diisocyanate compound which is a reaction product of a diol with a diisocyanate, for example, adduct of 1 mole of 1,3-butylene glycol and 2 moles of tolylene diisocyanate.
In the case where the diisocyanate compound represented by formula (1) has a crosslinkable group, examples of such a diisocyanate compound include a product obtained by addition-reacting a triisocyanate compound with one equivalent of a monofunctional alcohol or monofunctional amine compound having a crosslinkable group (for example, an ethylenically unsaturated bond group). Specific examples of the triisocyanate compound and the monofunctional alcohol or monofunctional amine compound having a crosslinkable group include those described in paragraphs [0034], [0035] and [0037] to [0040] of Japanese Patent No. 4,401,262, but the invention should not be construed as being limited thereto.
Specific examples of the diisocyanate compound having a crosslinkable group include those described in paragraphs [0042] to [0049] of Japanese Patent No. 4,401,262, but the invention should not be construed as being limited thereto.
(2) Diol Compound
Examples of the diol compound represented by formula (2) widely include a polyether diol compound, a polyester diol compound and a polycarbonate diol compound. The polyether diol compound includes compounds represented by formulae (3), (4), (5), (6) and (7) shown below, and a random copolymer of ethylene oxide and propylene oxide having a hydroxy group at the terminal.
Figure imgf000029_0001
Figure imgf000029_0002
HO-(CH2CH2C H2CH20)c— H (5)
HO-(CH2CH20)d— (CH2CHO)e— (CH2CH20)d-H (6)
CH3
Figure imgf000029_0003
In formulae (3) to (7), R14 represents a hydrogen atom or a methyl group, and X1 represents a group shown below, a, b, c, d, e, f and g each represents an integer of 2 or more and is preferably an integer from 2 to 100. Two ds may be the same or different. Also, two X's may be the same or different.
Figure imgf000029_0004
Specific examples of the polyether diol compound represented by formulae (3) and (4) include diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, heptaethylene glycol, octaethylene glycol, di-l,2-propylene glycol, tri-l,2-propylene glycol, tetra- 1,2-propylene glycol, hexa-l,2-propylene glycol, di- 1,3 -propylene glycol, tri- 1,3 -propylene glycol, tetra- 1,3 -propylene glycol, di-l,3-butylene glycol, tri-l,3-butylene glycol, hexa-l,3-butylene glycol, polyethylene glycol having weight average molecular weight of 1,000, polyethylene glycol having weight average molecular weight of 1,500, polyethylene glycol having weight average molecular weight of 2,000, polyethylene glycol having weight average molecular weight of 3,000, polyethylene glycol having weight average molecular weight of 7,500, polypropylene glycol having weight average molecular weight of 400, polypropylene glycol having weight average molecular weight of 700, polypropylene glycol having weight average molecular weight of 1,000, polypropylene glycol having weight average molecular weight of 2,000, polypropylene glycol having weight average molecular weight of 3,000 and polypropylene glycol having weight average molecular weight of 4,000.
Specific examples of the polyether diol compound represented by formula (5) include PTMG650, PTMG1000, PTMG2000 and PTMG3000 (produced by Sanyo Chemical Industries, Ltd.).
Specific examples of the polyether diol compound represented by formula (6) include NEWPOL PE-61, NEWPOL PE-62, NEWPOL PE-64, NEWPOL PE-68, NEWPOL PE-71, NEWPOL PE-74, NEWPOL PE-75, NEWPOL PE-78, NEWPOL PE-108, NEWPOL PE-128 and NEWPOL PE-61 (produced by Sanyo Chemical Ind., Ltd.).
Specific examples of the polyether diol compound represented by formula (7) include NEWPOL BPE-20, NEWPOL BPE-20F, NEWPOL BPE-20NK, NEWPOL BPE-20T, NEWPOL BPE-20G, NEWPOL BPE-40, NEWPOL BPE-60, NEWPOL BPE-100, NEWPOL BPE-180, NEWPOL BPE-2P, NEWPOL BPE-23P, NEWPOL BPE-3P and NEWPOL BPE-5P (produced by Sanyo Chemical Ind., Ltd.).
Specific examples of the random copolymer of ethylene oxide and propylene oxide having a hydroxy group at the terminal include NEWPOL 50HB-100, NEWPOL 50HB-260, NEWPOL 50HB-400, NEWPOL 50HB-660, NEWPOL 50HB-2000 and NEWPOL 50HB-5100 (produced by Sanyo Chemical Ind., Ltd.).
The polyester diol compound includes compounds represented by formulae (8) and (9) shown below.
Figure imgf000030_0001
O
HO-L4— (0-C-L5)n2-OH (9)
In formulae (8) and (9), L2, L3 and L4 each represents a divalent aliphatic or aromatic hydrocarbon group, and L5 represents a divalent aliphatic hydrocarbon group. L2, L3 and L5 may be the same as or different from each other. Preferably, each of L2 to L4 represents an alkylene group, an alkenylene group, an alkynylene group or an arylene group, and L5 preferably represents an
2 5
alkylene group. In L to L , other bond or functional group incapable of reacting with an isocyanate group, for example, an ether bond, a carbonyl bond, an ester bond, a cyano group, an olefin bond, a urethane bond, an amido group, a ureido group or a halogen atom may be present, nl and n2 each represents an integer of 2 or more, and preferably an integer from 2 to 100.
The polycarbonate diol compound includes a compound represented by formula (10) shown below. o
HO-L6— (0-C-L6)n3— OH (10)
In formula (10), L6s, which may be the same or different, each represents a divalent aliphatic or aromatic hydrocarbon group. L6 preferably represents an alkylene group, an alkenylene group, an alkynylene group or an arylene group. In L6, other bond or functional group incapable of reacting with an isocyanate group, for example, an ether bond, a carbonyl bond, an ester bond, a cyano group, an olefin bond, a urethane bond, an amido group, a ureido group or a halogen atom may be present. n3 represents an integer of 2 or more, preferably an integer from 2 to 100.
Specific examples of the diol compounds represented by formulae (8), (9) and (10) include Compound Nos. 1 to 18 set forth below. In the specific examples, n represents an integer of 2 or more.
Figure imgf000032_0001
( No.6)
Figure imgf000033_0001
Figure imgf000033_0002
( No.
Figure imgf000033_0003
( No. 9 )
HO-(CH2)6— (OCO(CH2)6)irOH
( No. 1 0)
HO-(CH2)5— {000(ΟΗ2)5)ΪΓΟΗ
( No.
Figure imgf000033_0004
( No. 1 2 )
HO -oca OH ( o.
Figure imgf000034_0001
( No.
Figure imgf000034_0002
( No.
Figure imgf000034_0003
( No. 1 6 )
Figure imgf000034_0004
( No.
Figure imgf000034_0005
( No.
Figure imgf000034_0006
m = 2 , 4
For the synthesis of the urethane resin, in addition to the diol compound described above, a diol compound having a substituent incapable of reacting with an isocyanate group may also be used in combination. Such a diol compound includes, for example, compounds represented by formulae (11) and (12) shown below.
HO-L7-0-CO-L8-CO-0-L7-OH (11)
HO-L8-CO-0-L7-OH (12) 7 8
In formulae (11) and (12), L and L , which may be the same or different, each represents a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group or a divalent
7 8
heterocyclic group. In L and L , other bond or functional group incapable of reacting with an isocyanate group, for example, a carbonyl bond, an ester bond, a urethane bond, an amido group or a ureido group may be present, if desired. Alternatively, L7 and L8 may be combined with each other to form a ring.
The divalent aliphatic hydrocarbon group, aromatic hydrocarbon group and heterocyclic group may have a substituent, and examples of the substituent include an alkyl group, an aralkyl group, an aryl group, an alkoxy group, an aryloxy group and a halogen atom, for example, -F, -CI, -Br or -I.
At least one of the diol compounds is preferably a diol compound having an acid group, as the diol compound having a substituent incapable of reacting with an isocyanate group described above. Specific examples of the acid group include those described above and the acid group is preferably a carboxylic acid group. The diol compound having a carboxylic acid group includes, for example, compounds represented by formulae (13) to (15) shown below.
Figure imgf000035_0001
Figure imgf000035_0002
Figure imgf000035_0003
In formulae (13) to (15), R15 represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, an alkoxy group or an aryloxy group, preferably a hydrogen atom, an alkyl group having from 1 to 8 carbon atoms or an aryl group having from 6 to 15 carbon atoms.
The alkyl group, aralkyl group, aryl group, alkoxy group and aryloxy group may have a substituent and examples of the substituent include a cyano group, a nitro group, a halogen atom, for' example, -F, -CI, -Br or -I, -CONH2, -COOR16, -OR16, -NHCONHR16, -NHCOOR16, -NHCOR16 and -OCONHR16 (wherein R16 represents an alkyl group having from 1 to 10 carbon atoms or an aralkyl group having from 7 to 15 carbon atoms).
L9, L10 and L11, which may be the same or different, each represents a single bond or a divalent aliphatic or aromatic hydrocarbon group, preferably an alkylene group having from 1 to 20 carbon atoms or an arylene group having from 6 to 15 carbon atoms, and more preferably an alkylene group having from 1 to 8 carbon atoms.
The divalent aliphatic or aromatic hydrocarbon group may have a substituent and examples of the substituent include an alkyl group, an aralkyl group, an aryl group, an alkoxy group and a halogen atom.
If desired, L9 to L11 may have other functional group incapable of reacting with an isocyanate group, for example, a group containing a carbonyl, ester, urethane, amido, ureido or ether group. Two or three of R15, L7, L8 and L9 may be combined with each other to form a ring.
Ar represents a trivalent aromatic hydrocarbon group which may have a substituent, and preferably represents an aromatic group having from 6 to 15 carbon atoms.
Specific examples of the diol compound having a carboxyl group represented by formulae (13) to (15) include 3,5-dihydroxybenzoic acid, 2,2-bis(hydroxymethyl)propionic acid, 2,2-bis(2-hydroxyethyl)propionic acid, 2,2-bis(3-hydroxypropyl)propionic acid, bis(hydroxymethyl)acetic acid, bis(4-hydroxyphenyl)acetic acid, 2,2-bis(hydroxymethyl)butyric acid, 4,4-bis(4-hydroxyphenyl)pentanoic acid, tartaric acid, N,N-dihydroxyethylglycine, and N,N-bis(2-hydroxyethyl)-3 -carboxypropionamide.
The presence of such a carboxyl group is preferred because properties, for example, a hydrogen-bonding property and alkali solubility can be imparted to the polyurethane resin.
A polyurethane resin having a carboxyl group in an amount of 0.5 to 4.0 meq/g, preferably from 1.0 to 3.0 meq/g, is one preferred embodiment of the polyurethane resin.
In the case where the diol compound represented by formula (2) has a crosslinkable group, a method using a diol compound having an unsaturated group as a raw material for the production of polyurethane resin is also suitable. Such a diol compound may be a commercially available product, for example, trimethylolpropane monoallyl ether or may be a compound easily produced by a reaction of a halogenated diol compound, a triol compound or an aminodiol compound with a carboxylic acid, acid chloride, isocyanate, alcohol, amine, thiol or alkyl halide compound having an unsaturated group. Specific examples of the diol compound having a crosslinkable group include compounds described in paragraphs [0057] to [0066] of Japanese Patent No. 4,401,262, but the invention should not be construed as being limited thereto.
Compound Nos. 13 to 17 set forth above correspond to the diol compound represented by formula (8), (9) or (10) and are also the diol compound having a crosslinkable group.
A polyurethane resin having a crosslinkable group in an amount of 0.5 meq/g or more, more preferably from 1.0 to 3.0 meq/g, is one preferred embodiment of the polyurethane resin.
For the synthesis of the urethane resin, in addition to the diol described above, a compound obtained by ring-opening of tetracarboxylic acid dianhydiide represented by any one of formulae (16) to (18) shown below with a diol compound may also be used in combination.
Figure imgf000037_0001
Figure imgf000037_0002
In the formulae (16) to (18), L represents a single bond, a divalent aliphatic or aromatic hydrocarbon group which may have a substituent (preferably, for example, an alkyl group, an aralkyl group, an aryl group, an alkoxy group, a halogeno group, an ester group or an amido group), -CO-, -SO-, -S02-, -O- or -S-, and preferably represents a single bond, a divalent aliphatic hydrocarbon group having from 1 to 15 carbon atoms, -CO-, -S02-, -O- or -S-.
The divalent aliphatic or aromatic hydrocarbon group may have a substituent, and examples of the substituent include an alkyl group, an aralkyl group, an aryl group, an alkoxy group, a halogen . atom, an ester bond-containing group (for example, an alkylcarbonyloxy group, an alkyloxycarbonyl group, an arylcarbonyloxy group or an aryloxycarbonyl group) and an amido group.
R" and R , which may be the same or different, each represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, an alkoxy group or a halogeno group, preferably a hydrogen atom, an alkyl group having from 1 to 8 carbon atoms, an aryl group having from 6 to 15 carbon atoms, an alkoxy group having from 1 to 8 carbon atoms or a halogeno group.
Two ofL12, R17 and R18 may be combined with each other to form a ring.
R19 and R20, which may be the same or different, each represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group or a halogeno group, preferably a hydrogen atom, an alkyl group having from 1 to 8 carbon atoms or an aryl group having from 6 to 15 carbon atoms.
12 19 20
Two of L , R' and R u may be combined with each other to form a ring.
L13 and L14, which may be the same or different, each represents a single bond, a double bond or a divalent aliphatic hydrocarbon group, preferably a single bond, a double bond or a methylene group. A represents a mononuclear or multinuclear aromatic ring, preferably an aromatic ring having from 6 to 18 carbon atoms.
Specific examples of the compounds represented by formulae (16), (17) and (18) include an aromatic tetracarboxylic dianhydnde, for example, pyromellitic dianhydnde,
3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenyltetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 4,4'-sulfonyldiphthalic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride,
bis(3 ,4-dicarboxyphenyl)ether dianhydride,
4,4'-[3,3'-(alkylphosphoryldiphenylene)-bis(iminocarbonyl)]diphthalic dianhydride,
adduct of hydroquinone diacetate and trimellitic anhydride or adduct of diacetyldiamine and trimellitic anhydride; an alicyclic tetracarboxylic dianhydride, for example,
5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-l ,2-dicarboxylic anhydride (EPICLON B-4400, produced by Dainippon Ink and Chemicals, Inc.), 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride or tetrahydrofurantetracarboxylic dianhydride; and an aliphatic tetracarboxylic dianhydride, for example, 1,2,3,4-butanetetracarboxylic dianhydride or 1 ,2,4,5-pentanetetracarboxylic dianhydride.
Examples of the method for introducing a compound obtained by ring-opening of the tetracarboxylic dianhydride with a diol compound into a polyurethane resin include: a) a method of reacting a diisocyanate compound with an alcohol-terminated compound obtained by ring-opening of the tetracarboxylic dianhydride with a diol compound, and b) a method of reacting the tetracarboxylic dianhydride with an alcohol-terminated urethane compound obtained by reacting a diisocyanate compound under diol compound-excess conditions.
Specific examples of the diol compound used for the ring-opening reaction include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, neopentyl glycol, 1,3-butylene glycol, 1,6-hexanediol, 2-butene-l,4-diol, 2,2,4-trirnethyl-l ,3-pentanediol,
1 ,4-bis-P-hydroxyethoxycyclohexane, cyclohexanedimethanol, tricyclodecanedimethanol, hydrogenated bisphenol A, hydrogenated bisphenol F, an ethylene oxide adduct of bisphenol A, a propylene oxide adduct of bisphenol A, an ethylene oxide adduct of bisphenol F, a propylene oxide adduct of bisphenol F, an ethylene oxide adduct of hydrogenated bisphenol A, a propylene oxide adduct of hydrogenated bisphenol A, hydroquinone dihydroxyethyl ether, p-xylylene glycol, dihydroxyethylsulfone, bis(2-hydroxyethyl)-2,4-tolylene dicarbamate,
2,4-tolylene-bis(2-hydroxyethylcarbamide), bis(2-hydroxyethyl)-m-xylylene dicarbamate and bis(2-hydroxyethyl)isophthalate.
The urethane resin described above is synthesized by adding the diisocyanate compound and the diol compound together with a known catalyst having an activity according to the reactivities of respective compounds in an aprotic solvent and heating the solution. The molar ratio (Ma: Mb) between the diisocyanate compound and the diol compound used for the synthesis is preferably from 1 : 1 to 1.2 : 1. It is preferred that a product having the desired physical property, for example, molecular weight or viscosity is finally synthesized in the form of containing no residual isocyanate group by undergoing treatment with an alcohol, amine or the like.
A urethane resin having a crosslinkable group (for example, an unsaturated group) in the terminal or main chain of the polymer is also suitably used. By having a crosslinkable group in the terminal or main chain of the polymer, the crosslinking reactivity between the polymerizable compound and the urethane resin or between the urethane resins is enhanced so that the strength of the infrared ray shielding film in which the pattern is formed is increased. It is particularly preferred that the unsaturated group has a carbon-carbon double bond because of easy occurrence of the crosslinking reaction.
The method for introducing a crosslinkable group into the polymer terminal includes the following method. Specifically, the introduction may be attained by using an alcohol, amine or the like having a crosslinkable group in the step of treating the residual isocyanate group in the polymer terminal with an alcohol, amine or the like in the process for the synthesis of urethane resin described above. Specific examples of the compound include the compounds described above as the monofunctional alcohol or monofunctional amine compound having a crosslinkable group.
The crosslinkable group is more preferably introduced into the polymer side chain than into the polymer terminal from the standpoint in that the introduction amount is easily controlled, in that the introduction amount can be increased and in that the crosslinking reaction efficiency is enhanced.
The method for introducing a crosslinkable group into the main chain includes a method where a diol compound having an unsaturated group in the main chain direction is used for the synthesis of the urethane resin. Specific examples of the diol compound having an unsaturated group in the main chain direction include cis-2-butene-l,4-diol, trans-2-butene-l,4-diol and polybutadiene diol.
As the alkali-soluble binder other than the (meth)acrylic resin and urethane resin, acetal-modified polyvinyl alcohol binder polymers having an acid group described, for example, in European Patents 993,966 and 1,204,000 and JP-A-2001-318463 are suitable because of excellence balance between the film strength and development property. In addition, polyvinylpyrrolidone, polyethylene oxide or the like is useful as a water-soluble linear organic polymer. Further, for increasing the strength of the cured film, alcohol-soluble nylon, a polyether of 2,2-bis(4-hydroxyphenyl)propane and epichlorohydrin or the like is also useful.
In particular, a [benzyl (meth)acrylate/(meth)acrylic acid/and, if desired, other addition-polymerizable vinyl monomer] copolymer or an [allyl (meth)acrylate/(meth)acrylic acid/and, if desired, other addition-polymerizable vinyl monomer] copolymer is suitable because of excellent balance of the film strength, sensitivity and development property.
The weight average molecular weight of the binder polymer which can be used in the infrared ray shielding composition according to the invention is preferably 3,000 or more, more preferably in a range from 5,000 to 300,000, and most preferably in a range from 10,000 to 30,000, and the number average molecular weight thereof is preferably 1,000 or more, and more preferably in a range from 2,000 to 250,000. The polydispersity (weight average molecular weight/number average molecular weight) is preferably 1 or more, and more preferably in a range from 1.1 to 10.
The alkali-soluble binder may be any of a random polymer, a block polymer, a graft polymer or the like.
The binder (preferably alkali-soluble binder) can be synthesized by a conventionally known method. Examples of the solvent used at the synthesis include tetrahydrofuran, ethylene dichloride, cyclohexanone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate and butyl acetate. The solvents may be used individually or as a mixture of two or more thereof.
The binders may be used individually or in combination of two or more thereof.
The content of the binder is preferably from 5 to 80% by weight, more preferably from 30 to 60% by weight, based on the total solid content of the infrared ray shielding composition according to the invention. When the content of the binder is in the range described above, the exposure sensitivity is good, the processing is conducted for only a short time, and good thermal cycle test resistance (TCT resistance) is obtained.
[5] Infrared ray blocking agent other than fine particle of tungsten oxide containing alkali metal The infrared ray shielding composition according to the invention may contain an infrared ray blocking agent (hereinafter, also referred to as "other infrared ray blocking agent") other than the fine particle of tungsten oxide containing an alkali metal within the range not impairing the effects of the invention. The other infrared ray blocking agent is preferably a compound having absorption in a wavelength range from 800 to 1,200 nm and exhibiting good transparency to light used for exposure. From such a standpoint, the other infrared ray blocking agent is preferably selected from an infrared absorbing dye and an infrared absorbing inorganic pigment.
Examples of the infrared absorbing dye include a cyanine dye, a phthalocyanine dye, a naphthalocyanine dye, an immonium dye, an aminium dye, a quinolium dye, a pyrylium dye and a metal complex dye, for example, aNi complex dye.
The dye usable as the infrared ray blocking agent is also available as a commercial product, and suitable examples thereof include the following commercially available dyes:
S0345, S0389, S0450, S0253, S0322, S0585, S0402, S0337, S0391 , S0094, S0325, S0260, S0229, S0447, S0378, S0306 and S0484, produced by FEW Chemicals GmbH;
ADS795WS, ADS805WS, ADS819WS, ADS820WS, ADS823WS, ADS830WS, ADS850WS, ADS845MC, ADS870MC, ADS880MC, ADS890MC, ADS920MC, ADS990MC, ADS805PI, ADSW805PP, ADS810CO, ADS813MT, ADS815EI, ADS816EI, ADS818HT, ADS819MT, ADS819MT, ADS821NH, ADS822MT, ADS838MT, ADS840MT, ADS905AM, ADS956BP, ADS1040P, ADS1040T, ADS1045P, ADS1040P,ADS1050P, ADS1065 A, ADS1065P, ADS1100T and ADS1120F, by American Dye Source, Inc.;
YKR-4010, YKR-3030, YK -3070, MIR-327, MIR-371, SIR-159, PA-1005, MIR-369, MIR-379, SIR-128, PA-1006, YKR-2080, MIR-370, YKR-3040, YKR-3081, SIR-130, MIR-362, YKR-3080, SIR-132 and PA-1001, produced by Yamamoto Chemicals Inc.; and
NK-123, NK-124, NK-1144, N -2204, N -2268, NK-3027, NKX-113, NKX-1199, NK-2674, NK-3508, NKX-114, NK-2545, NK-3555, NK-3509 and NK-3519, produced by Hayasbibara Biochemical Labs, Inc.
Of the dyes, a phmalocyanine dye and a metal complex dye are preferred from the standpoint of heat resistance.
The dyes may be used individually, or for the purpose of exhibiting a good light shielding property in a wavelength range from 800 to 1,200 nm, two or more of the dyes may be used in combination according to the purpose.
Examples of the infrared absorbing inorganic pigment usable as the other infrared ray blocking agent include zinc flower, lead white, lithopone, titanium oxide, chromium oxide, iron oxide, sedimentating barium sulfate, barite powder, red lead, iron oxide red, lead yellow, zinc yellow (zinc yellow class 1, zinc yellow class 2), ultramarine blue, Prussia blue (iron/potassium ferrocyanide), zircon grey, praseodymium yellow, chrome-titanium yellow, chrome green, peacock, Victoria green, iron blue (irrelevant to Prussia blue), vanadium-zirconium blue, chrome-tin pink, manganese pink and salmon pink. Further, examples of the black pigment which can be used include a metal oxide, a metal nitride or a mixture thereof, containing one or two or more metal elements selected from the group consisting of Co, Cr, Cu, Mn, Ru, Fe, Ni, Sn, Ti and Ag.
The black pigment is preferably titanium black which is a black pigment containing titanium nitride because of its good blocking property in the infrared region of a wavelength from 800 to 1,200 nm.
The titanium black can be obtained by a known method. Also, as a commercially available product, titanium black produced, for example, by Ishihara Sangyo Kaisha, Ltd., Ako Kasei Co., Ltd., JEMCO Inc., Mitsubishi Materials Corp. or Mitsubishi Materials Electronic Chemicals Co., Ltd. may be used.
The titanium black indicates a black particle containing titanium atom. It is preferably low-order titanium oxide, titanium oxynitride or the like. As the titanium black particle, a particle whose surface is modified for the purposes, for example, of enhancing the dispersibility or inhibiting aggregation may be used, if desired.
The surface modification method includes a method of covering the surface with one or more oxides selected from silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide and zirconium oxide. Also, the surface may be treated with a water-repellent substance as described in paragraphs [0010] to [0027] of JP-A-2007-302836.
Examples of the method for producing titanium black include a method of heating and reducing a mixture of titanium dioxide and metal titanium in a reductive atmosphere (see, JP-A-49-5432), a method of reducing ultrafine titanium dioxide obtained by high-temperature hydrolysis of titanium tetrachloride, in a reductive atmosphere containing hydrogen (see, JP-A-57-205322), a method of reducing titanium dioxide or titanium hydroxide at high temperature in the presence of ammonia (see, JP-A-60-65069 and JP-A-61-201610), and a method of attaching a vanadium compound to titanium dioxide or titanium hydroxide and then reducing it at high temperature in the presence of ammonia (see, JP-A-61-201610), but the method should not be construed as being limited thereto.
The particle size of the titanium black particle is not particularly restricted and is preferably from 3 to 2,000 nm, more preferably from 10 to 500 nm, from the standpoint of dispersibility and colorability.
The specific surface area of titanium black is not particularly restricted and a value measured by a BET method is ordinarily approximately from 5 to 150 m /g, preferably approximately from 20 to 100 m /g, in order to obtain a predetermined water-repellent property after the surface treatment of titanium black with a water repelling agent.
The particle size of the inorganic pigment used as the other infrared ray blocking agent is, in terms of the average particle size, preferably from 3 nm to 0.01 mm, and from the standpoint of dispersibility, light-shielding property and sedimentation property with lapse of time, the average particle size is preferably from 10 nm to 1 μηι.
The infrared ray shielding composition according to the invention may or may not contain the other infrared ray blocking agent, and in the case of containing the other infrared ray blocking agent, the content thereof is preferably from 5 to 75% by weight, more preferably from 10 to 40% by weight, based on the weight of the fine particle of tungsten oxide containing an alkali metal.
[6] Dispersing agent
In the invention, the fine particle of tungsten oxide containing an alkali metal may be dispersed to use employing a known dispersing agent for the purpose of enhancing dispersibility and dispersion stability of the fine particle of tungsten oxide in the infrared ray shielding composition.
The dispersing agent which can be used in the invention includes a polymer dispersing agent (for example, polyamidoamine and salt thereof, polycarboxylic acid and salt thereof, a high molecular weight unsaturated acid ester, a modified polyurethane, a modified polyester, a modified poly(meth)acrylate, a (meth)acrylic copolymer or a naphthalenesulfonic acid-formalin condensate), and a surfactant, for example, a polyoxyethylene alkyl phosphate ester, a polyoxyethylene alkylamine or an alkanolamine.
The polymer dispersing agent can be further classified into a straight-chain polymer, a terminal-modified polymer, a graft polymer and a block polymer according to its structure.
Examples of the terminal-modified polymer having an anchor moiety to the surface include polymers having a phosphoric acid group at the terminal described in JP-A-3- 112992 and JP-T-2003-533455 (the term "JP-T" as used herein means a published Japanese translation of a PCT patent application), polymers having a sulfonic acid group at the terminal described in JP-A-2002-273191, polymers having an organic dye partial structure or a heterocyclic ring described in JP-A-9-77994 and polymers produced by modifying an oligomer or polymer having a hydroxy group or an amino group at one terminal with an acid anhydride described in JP-A-2008-29901. A polymer in which two or more anchor moieties (for example, an acid group, a basic group, an organic dye partial structure or a heterocyclic ring) to the surface of infrared ray blocking agent are introduced into the polymer terminal described in JP-A-2007-277514 is also preferred because of its excellent dispersion stability. Examples of the graft polymer having an anchor moiety to the surface include reaction products of a poly(lower alkylene imine) and a polyester described in JP-A-54-37082, JP-T-8-507960 and JP-A-2009-258668, reaction products of a polyallylamine and a polyester described in JP-A-9- 169821, amphoteric dispersing resins having a basic group and an acidic group described in JP-A-2009-203462, copolymers of a macromonomer and a nitrogen atom-containing monomer described in JP-A-10-339949 and JP-A-2004-37986, graft polymers having an organic dye partial structure or a heterocyclic ring described in JP-A-2003-238837, JP-A-2008-9426 and JP-A-2008-81732 and copolymers of a macromonomer and an acid group-containing monomer described in JP-A-2010-106268.
As to the macromonomer used when producing a graft polymer having an anchor moiety to the surface by radical polymerization, a known macromonomer may be used and examples thereof include MACROMONOMER AA-6 (a polymethyl methacrylate having a terminal group of a methacryloyl group), AS-6 (a polystyrene having a terminal group of a methacryloyl group), AN-6S (a copolymer of an acrylonitrile and a styrene having a terminal group of a methacryloyl group) and AB-6 (a polybutyl acrylate having a terminal group of a methacryloyl group) produced by Toagosei Co., Ltd.; PLACCEL FM5 (a 5 molar equivalent adduct of ε-caprolactone to 2-hydroxyethyl methacrylate) and FA10L (a 10 molar equivalent adduct of ε-caprolactone to 2-hydroxyethyl acrylate) produced by Daicel Corp.; and a polyester macromonomer described in JP-A-2-272009. Among them, a polyester macromonomer excellent in flexibility and solvent affinity is preferred from the standpoint of dispersibility and dispersion stability of the infrared ray blocking agent in the infrared ray shielding composition, and a polyester macromonomer represented by the polyester macromonomer described in JP-A-2-272009 is most preferred.
As to the block polymer having an anchor moiety to the surface, block polymers described, for example, in JP-A-2003-491 10 and JP-A-2009-52010 are preferred.
The dispersing agent which can be used may be appropriately selected, for example, from known dispersing agents and surfactants.
Specific examples thereof include Disperbyk-101 (polyarnidoarnine phosphate), 107 (carboxylic acid ester), 110 (copolymer containing an acid group), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (high molecular weight copolymer) and BYK-P104, PI 05 (high molecular weight unsaturated polycarboxylic acid) produced by Byk-Chemie; EFKA 4047, 4050-4010-4165 (polyurethane-based), EFKA 4330-4340 (block copolymer), 4400-4402 (modified polyacrylate), 5010 (polyester amide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester) and 6745 (phthalocyanine derivative) produced by EFKA; AJISPER PB821, PB822, PB880 and PB881 produced by Ajinomoto Fine Techno Co., Inc.; FLOWLEN TG-710 (urethane oligomer) and POLYFLOW No. 50E and No. 300 (acrylic copolymer) produced by Kyoeisha Chemical Co., Ltd.; DISPERON KS-860, 873SN, 874, #2150 (aliphatic polyvalent carboxylic acid), #7004 (polyetherester), DA-703-50, DA-705 and DA-725 produced by Kusumoto Chemicals Ltd.; DEMOL RN, N (naphthalenesulfonic acid-formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid-formalin polycondensate), HOMOGENOL L-18 (high molecular weight polycarboxylic acid), EMULGEN 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether) and ACETAMIN 86 (stearylamine acetate) produced by Kao Corp.; SOLSPERSE 5000 (phthalocyanine derivative), 13240 (polyester amine), 3000, 17000, 27000 (polymer having a functional moiety at terminal), 24000, 28000, 32000, 38500 (graft polymer) produce by Lubrizol Japan Ltd.; NIKKOL T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) produced by Nikko Chemicals Co., Ltd.; HINOACT T-8000E produced by Kawaken Fine Chemicals Co., Ltd.; Organosiloxane Polymer KP341 produced by Shin-Etsu Chemical Co., Ltd.; a cationic surfactant, for example, W001, a nonionic surfactant, for example, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate or sorbitan fatty acid ester and an anionic surfactant, for example, W004, W005 or W017 produced by Yusho Co., Ltd.); EFKA-46, EFKA-47, EFKA-47EA, EFKA Polymer 100, EFKA Polymer 400, EFKA Polymer 401 and EFKA Polymer 450 produced by Morishita & Co., Ltd.; a polymer dispersing agent, for example, DISPERSE AID 6, DISPERSE AID 8, DISPERSE AID 15 and DISPERSE AID 9100 produced by San Nopco Ltd.; ADEKA PLURONIC L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121 and P-123 produced by ADEKA Corp.; and IONET S-20 produced by Sanyo Chemical Industries, Co., Ltd.
The dispersing agents may be used individually or in combination of two or more thereof. As to the dispersing agent according to the invention, the terminal-modified polymer, graft polymer or block polymer having an anchor moiety to the surface of the infrared ray blocking agent may be also used in combination with an alkali-soluble resin. Examples of the alkali-soluble resin include a (meth)acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, a partially esterified maleic acid copolymer, an acidic cellulose derivative having a carboxylic acid in its side chain and a resin obtained by modifying a hydroxy group-containing polymer with an acid anhydride, and particularly a (meth)acrylic acid copolymer is preferred. Also, N-position substituted maleimide monomer copolymers described in JP-A- 10-300922, ether dimer copolymers described in JP-A-2004-300204 and polymerizable group-containing alkali-soluble resins described in JP-A-7-319161 are preferred.
From the standpoint of dispersibility and sedimentation property, resins described in JP-A-2010-106268 shown below are preferred. In particular, from the standpoint of dispersibility, a polymer dispersing agent having a polyester chain in its side chain is preferred, and a resin having an acid group and a polyester chain is also suitable. As to the acid group in the dispersing agent, in view of adsorptivity, an acid group having a pKa of 6 or less is preferred, and a carboxylic acid, a sulfonic acid or a phosphoric acid is more preferred.
Dispersing resins described in JP-A-2010-106268, which are preferably used in the invention, are described below.
The dispersing agent is preferably a graft copolymer having a graft chain selected from a polyester structure, a polyether structure and a polyacrylate structure, in which the number of atoms excluding hydrogen atoms is from 40 to 10,000, and the graft copolymer preferably contains at least a structural unit represented by any of formulae (1) to (4) shown below, more preferably contains at least a structural unit represented by any of formulae (1 A), (2A), (3A), (3B) and (4) shown below.
Figure imgf000046_0001
atom or a monovalent organic group, and from the standpoint of restriction on the synthesis, is preferably a hydrogen atom or an alkyl group having from 1 to 12 carbon atoms, more preferably a hydrogen atom or a methyl group, and particularly preferably a methyl group.
In formulae (1) to (4), W1, W2, W3 and W4 each independently represents an oxygen atom or NH, and particularly preferably an oxygen atom.
In formulae (1) to (4), Y1, Y2, Y3 and Y4 each independently represents a divalent connecting group and is not particularly restricted in its structure. Specific examples thereof include Connecting groups (Y-l) to (Y-20) shown below. In the structures below, A and B indicate bonds to the left terminal group and the right terminal group in formulae (1) to (4), respectively. Of the structures shown below, (Y-2) and (Y-13) are preferred from the standpoint of ease in synthesis.
Figure imgf000047_0001
(Y-l ) (Y-2) (Y-3)
A (Y-4) (Y-5) (Y-6)
Figure imgf000047_0002
In formulae (1) to (4), Z1, Z2, Z3 and Z4 each independently represents a hydrogen atom or a monovalent substituent, and the structure of the substituent is not particularly restricted. Specific examples thereof include an alkyl group, a hydroxy group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group and an amino group. Among them, from the standpoint of enhancing the dispersibility, the substituent having a steric repulsion effect is preferred. The monovalent substituent represented by any of Z1 to Z3 is preferably an alkyl group having from 5 to 24 carbon atoms or an alkoxy group having from 5 to 24 carbon atoms and particularly, an alkoxy group having a branched alkyl group having from 5 to 24 carbon atoms or an alkoxy group having a cyclic alkyl group having from 5 to 24 carbon atoms is preferred. The monovalent substituent represented by any of Z4 is preferably an alkyl group having from 5 to 24 carbon atoms and particularly, a branched alkyl group having from 5 to 24 carbon atoms or a cyclic alkyl group having from 5 to 24 carbon atoms is preferred.
In formulae (1) to (4), n, m, p and q each represents an integer from 1 to 500.
In formulae (1) and (2), j and k each independently represents an integer from 2 to 8. From the standpoint of dispersion stability, each of j and k in formulae (1) and (2) is preferably an integer from 4 to 6, and most preferably 5.
In formula (3), R' represents a branched or straight-chain alkylene group. R' in formula (3) is preferably an alkylene group having from 1 to 10 carbon atoms, and more preferably an alkylene group having 2 or 3 carbon atoms.
Also, as to R' in formula (3), two or more R's having different structures may be mixed to use in the dispersing resin.
In formula (4), R represents a hydrogen atom or a monovalent organic group and is not particularly restricted in its structure. R is preferably a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, more preferably a hydrogen atom or an alkyl group. When R is an alkyl group, the alkyl group is preferably a straight-chain alkyl group having from 1 to 20 carbon atoms, a branched alkyl group having from 3 to 20 carbon atoms or a cyclic alkyl group having from 5 to 20 carbon atoms, more preferably a straight-chain alkyl group having from 1 to 20 carbon atoms, and particularly preferably a straight-chain alkyl group having from 1 to 6 carbon atoms.
Also, as to R in formula (4), two or more Rs having different structures may be mixed to use in the specific resin.
From the standpoint of dispersion stability, the structural unit represented by formula (1) is more preferably a structural unit represented by formula (1 A) shown below.
Also, from the standpoint dispersion stability, the structural unit represented by formula (2) is more preferably a structural unit represented by formula (2A) shown below.
Figure imgf000049_0001
In formula (1A), X1, Y1, Z1 and n have the same meanings as X1, Y1, Z1 and n in formula
(1) , and preferred ranges are also the same.
In formula (2A), X2, Y2, Z2 and m have the same meanings as X2, Y2, Z2 and m in formula
(2) , and preferred ranges are also the same.
Also, from the standpoint dispersion stability, the structural unit represented by formula (3) is more preferably a structural unit represented by formula (3A) or (3B) shown below.
Figure imgf000049_0002
(3A> (3B)
In formula (3A) or (3B), X3, Y3, Z3 and p have the same meanings as X3, Y3, Z3 and p in formula (3), and preferred ranges are also the same.
Specific examples thereof include compounds set forth below. In the compounds set forth below, the numerical value attached to each structural unit (the numerical value attached to the repeating unit of the main chain) indicates the content (% by weight, shown as (wt%)) of the structural unit. The numerical value attached to the repeating unit of the side chain indicates the number of repetitions of the repeating unit.
Figure imgf000049_0003
Figure imgf000050_0001
(Compound 2)
Figure imgf000050_0002
O
(Compound 3)
Figure imgf000050_0003
(Compound 4)
Figure imgf000051_0001
(Compound 5)
Figure imgf000051_0002
(Compound 6)
Figure imgf000051_0003
(Compound 7)
Figure imgf000051_0004
(Compound 8)
Figure imgf000052_0001
o
(Compound 9)
Figure imgf000052_0002
(n=5— 20)
(Compound 11)
Figure imgf000052_0003
Figure imgf000053_0001
(Compound 13)
Figure imgf000053_0002
O
(Compound 14)
0
Figure imgf000053_0003
Me
(Compound 15)
Figure imgf000053_0004
(Compound 16)
Figure imgf000054_0001
(Compound 20)
Figure imgf000054_0002
(Compound 21)
Figure imgf000054_0003
(Compound 22)
Figure imgf000055_0001
(Compound 23)
Figure imgf000055_0002
(Compound 24)
Figure imgf000055_0003
(Compound 25)
Figure imgf000056_0001
e
(Compound 26)
Figure imgf000056_0002
(Compound 27)
Figure imgf000056_0003
(Compound 28)
Figure imgf000057_0001
Figure imgf000057_0002
Figure imgf000057_0003
o o
(Compound 31)
Figure imgf000058_0001
(Compound 32)
Figure imgf000058_0002
Figure imgf000058_0003
(Compound 34)
Figure imgf000058_0004
(Compound 35)
Figure imgf000059_0001
(Compound 36)
Figure imgf000059_0002
OH OH
(Compound 37)
Figure imgf000059_0003
(Compound 38)
Figure imgf000059_0004
(n=5—20)
(Compound 39)
Figure imgf000060_0001
(Compound 40)
Figure imgf000060_0002
(Compound 41)
Figure imgf000060_0003
(Compound 42)
Figure imgf000060_0004
(Compound 43)
Figure imgf000061_0001
(Compound 44)
Figure imgf000061_0002
(Compound 45)
Figure imgf000061_0003
(Compound 46)
Figure imgf000061_0004
(Compound 47)
Figure imgf000062_0001
(Compound 48)
Figure imgf000062_0002
(Compound 49)
Figure imgf000062_0003
(Compound 50)
Figure imgf000062_0004
o
(Compound 51)
Figure imgf000063_0001
Figure imgf000064_0001
Figure imgf000065_0001
Figure imgf000065_0002
Figure imgf000065_0003
Figure imgf000065_0004
(Compound 62)
Figure imgf000066_0001
Figure imgf000066_0002
Figure imgf000066_0003
Figure imgf000066_0004
(Compound 66)
Figure imgf000067_0001
Figure imgf000067_0002
(Compound 68)
Figure imgf000067_0003
(Compound 70)
Figure imgf000068_0001
Figure imgf000068_0002
In the case of using a dispersing agent, from the standpoint of enhancing the dispersibility, it is preferred to prepare a dispersion composition using the fine particle of tungsten oxide containing an alkali metal (and, if desired, the other infrared ray blocking agent described above), the dispersing agent and an appropriate solvent and then the dispersion composition is blended with the infrared ray shielding composition.
The infrared ray shielding composition according to the invention may or may not contain the dispersing agent, and in the case of containing the dispersing agent, the content thereof in the composition is preferably from 1 to 90 % by weight, more preferably from 3 to 70% by weight, based on the total solid content of the fine particle of tungsten oxide containing an alkali metal in the composition or, in the case of using other infrared ray blocking agent and using an infrared absorbing inorganic pigment as the other infrared ray blocking agent, based on the sum of the total solid content of the fine particle of tungsten oxide containing an alkali metal and the total solid content of the infrared absorbing inorganic pigment in the infrared ray shielding composition.
[7] Ultraviolet absorbing agent
The infrared ray shielding composition according to the invention may contain an ultraviolet absorbing agent.
The ultraviolet absorbing agent is incorporated, for example, into an infrared ray shielding composition for solder resist and after forming a photosensitive layer by coating the infrared ray shielding composition on a semiconductor substrate for solid-state imaging device where an alignment mark is provided on the surface, exposure and development are conducted to form a solder resist layer, whereby a solder resist layer capable of satisfying both solving the problem derived from reflected light on the substrate surface described below and ensuring detection performance of the alignment mark by a visible light sensor can be more reliably produced.
In the case where the substrate surface having provided thereon a photosensitive layer is formed of a material having high light reflectivity, for example, metal, since reflected light from the substrate surface in the exposure to the photosensitive layer becomes considerable, the cross-sectional shape of the obtained pattem is liable to become a skirt shape (that is, rectangularity of the cross-sectional shape is liable to be impaired). On the other hand, when the exposure amount is suppressed in order to reduce the reflected light, a pattern having a rectangular cross-sectional shape can be hardly formed because of the insufficient exposure amount.
However, in the case where the infrared ray shielding composition according to the invention contains the ultraviolet absorbing agent, even when irradiation is performed with an exposure amount necessary to obtain a pattern having a rectangular cross-sectional shape (hereinafter, also referred to as an "adequate exposure amount" sometimes), the ultraviolet absorbing agent absorbs the reflected light and thus, the infrared ray shielding composition containing the ultraviolet absorbing agent according to the invention is suitable for forming the pattem having a rectangular cross-sectional shape.
As the ultraviolet absorbing agent, any compound may be used as long as it satisfies the spectral characteristics described above. However, the ultraviolet absorbing agent indicates a compound having no function of initiating the polymerization of a polymerizable compound by light or heat (that is, a compound not falling under the category of a polymerization initiator). The term "having no function of initiating the polymerization of a polymerizable compound" as used herein means that even when the ultraviolet absorbing agent receives light or heat energy, it does not generate an active species for initiating the polymerization of a polymerizable compound.
More specifically, the ultraviolet absorbing agent is preferably a compound having no photosensitivity to an ultraviolet ray or visible light (more specifically, light having a wavelength from 300 to 450 nm) and having no thermosensitivity to heat (more specifically, for example, heat from 150 to 250°C). The terms "photosensitivity" and "thermosensitivity" as used herein mean to exhibit the intended function while accompanying change in the chemical structure by the ultraviolet ray or visible light or heat.
Further, the ultraviolet absorbing agent is preferably not only having no function of initiating the polymerization of a polymerizable compound but also having no properly of a sensitizer described below. The term "property of a sensitizer" as used herein means the properly of transferring energy obtained by light absorption of the sensitizer itself to other material (polymerization initiator, for example, the triazine polymerization initiator) and thereby initiating the polymerization.
The ultraviolet absorbing agent is preferably a compound having a maximum absorption wavelength in a range from 300 to 430 nm, and more preferably a compound having a maximum absorption wavelength in a range from 330 to 420 nm.
The ultraviolet absorbing agent still more preferably has a maximum absorption wavelength at least in one range of (I) range from 340 to 380 nm, (II) range from 380 to 420 nm and (III) range of from 420 to 450 nm.
At the time of forming a pattern by applying exposure and development to the photosensitive layer formed from the infrared ray shielding composition according to the invention, in the case where the light source for exposure contains i-line, the ultraviolet absorbing agent preferably has a maximum absorption wavelength in the wavelength range (I) described above.
In the case where the light source for exposure contains h-line, the ultraviolet absorbing agent preferably has a maximum absorption wavelength in the wavelength range (II) described above.
In the case where the light source for exposure contains g-line, the ultraviolet absorbing agent preferably has a maximum absorption wavelength in the wavelength range (III) described above.
As the ultraviolet absorbing agent, for example, a salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based or triazine-based ultraviolet absorbing agent can be used.
Examples of the salicylate-based ultraviolet absorbing agent include phenyl salicylate, p-octylphenyl salicylate and p-tert-butylphenyl salicylate. Examples of the benzophenone-based ultraviolet absorbing agent include 2,2'-dihydroxy-4-methoxybenzophenone,
2,2' -dihydroxy-4,4 ' -dimethoxybenzophenone, 2,2 ' ,4,4' -tetrahydroxybenzophenone,
2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone and
2-hydroxy-4-octoxybenzophenone. Examples of the benzotriazole-based ultraviolet absorbing agent include 2-(2' -hydroxy-3 ' ,5 '-di-tert-butylphenyl)-5-chlorobenzotriazole,
2-(2' -hydroxy-3 ' -tert-butyl-5 ' -methylphenyl)-5 -chlorobenzotriazole,
2-(2 ' -hydroxy-3 ' -tert-amyl-5 ' -isobutylphenyl)-5 -chlorobenzotriazole,
2-(2'-hydroxy-3'-isobutyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-propylphenyl)-5-chlorobenzotriazole,
2-(2' -hydroxy-3 ' ,5 ' -di-tert-butylphenyl)benzotriazole, 2-(2 ' -hydroxy-5 ' -methylphenyl)benzotriazole and 2- [2 ' -hydroxy-5 '-(1,1,3,3 -tetramethyl)phenyl]benzotriazole.
Examples of the substituted acrylonitrile-based ultraviolet absorbing agent include ethyl 2-cyano-3,3-diphenylacrylate and 2-ethylhexyl 2-cyano-3,3-diphenylacrylate. Examples of the triazine-based ultraviolet absorbing agent include a mono(hydroxyphenyl)triazine compound, for example,
2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dim-ethylphenyl)-l,3,5-tr iazine,
2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimemylphenyl)-l,3,5-tri azine and 2-(2,4-dmydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-l,3,5-triazine; a
bis(hydroxyphenyl)triazine compound, for example,
2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)- 1 ,3 ,5-triazine,
2,4-bis(2-hydroxy-3-memyl-4-propyloxyphenyl)-6-(4-memylphenyl)-l,3,5-triazine and
2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6-(2,4-dimethylphenyl)- 1 ,3,5-triazine; and a tris(hydroxyphenyl)triazine compound, for example,
2,4-bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-dibutoxyphenyl)-l,3,5-triazine,
2,4,6-tris(2-hydroxy-4-octyloxyphenyl)- 1 ,3,5-triazine and
2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropyloxy)phenyl]- 1 ,3 ,5-triazine.
In addition, a diethylamonopnenylsulfonyl pentadienoate-based ultraviolet absorbing agent (DPO, produced by FUJIFILM Finechemicals Co., Ltd.) or the like is also suitably used.
The ultraviolet absorbing agent is preferably a compound represented by formula (A) shown below.
Formula (A)
Figure imgf000071_0001
In formula (A), R$i and ¾2 each independently represents a hydrogen atom, an alkyl group or an aryl group, or and are combined with each other to represent a nonmetallic atomic group necessary for forming a 5-membered or 6-membered ring. Also, either one of R^t and ¾2 may be combined with the methine group next to the nitrogen atom to form a 5-membered or 6-membered ring. ¾ and Y6i each independently represents a cyano group, -COORa, -CONR63R64, -COR63, -S02R63 or -SC^R^i^, and R« and each independently represents a hydrogen atom, an alkyl group or an aryl group. ¾ and Y6i may be combined with each other to form a 5-membered or 6-membered ring. Further, any one of R6i, ¾2, όΐ and Y61 may be combined with any one of Rs\, !½, ¾ and Y61 in another compound represented by formula (A) to form a dimer.
Figure imgf000072_0001
In the invention, the various ultraviolet absorbing agents may be used individually or in combination of two or more thereof.
The infrared ray shielding composition according to the invention may or may not contain the ultraviolet absorbing agent, and in the case of containing the ultraviolet absorbing agent, the content thereof is preferably from 0.001 to 1% by weight, more preferably from 0.01 to 0.3% by weight, based on the total solid content of the infrared ray shielding composition according to the invention.
[8] Sensitizer
The infrared ray shielding composition according to the invention may contain a sensitizer for the purpose of increasing the radical generating efficiency of the triazine polymerization initiator and making the photosensitive wavelength longer. The sensitizer which can be used in the invention is preferably a compound capable of sensitizing the triazine polymerization initiator described above by an electron transfer mechanism or an energy transfer mechanism. The sensitizer which can be used in the invention includes compounds belonging to compound groups described below and having an absorption wavelength in the wavelength region from 300 to 450 nm.
Preferred examples of the sensitizer include compounds belonging to the following compound groups and having an absorption wavelength in the wavelength region from 330 to 450 nm.
For instance, preferred compounds include a multinuclear aromatic compound (for example, phenanthrene, anthracene, pyrene, perylene, triphenylene or 9,10-dialkoxyanthracene), a xanthene (for example, fluorescein, eosin, erythrosine, Rhodamine B or rose Bengal), a thioxanthone (2,4-diethylthioxanthone, isopropylthioxanthone, diethylthioxanthone or chlorothioxanthone), a cyanine (for example, thiacarbocyanine or oxacarbocyanine), a merocyanine (for example, merocyanine or carbomerocyanine), a phthalocyanine, a thiazine (for example, thionine, methylene blue or toluidine blue), an acridine (for example, acridine orange, chloroflavin or acriflavin), an anthraquinone (for example, anthraquinone), a squarylium (for example, squarylium), acridine orange, a coumarin (for example, 7-diemylammo-4-methylcoumarin), a ketocoumarin, a phenothiazine, a phenazine, a styrylbenzene, an azo compound, diphenylmethane, triphenylmethane, a distyrylbenzene, a carbazole, porphyrin, a spiro compound, quinacridone, indigo, styryl, a pyrylium compound, a pyrromethene compound, a pyrazolotriazole compound, a benzothiazole compound, a barbituric acid derivative, a thiobarbituric acid derivative, acetophenone, benzophenone, a thioxanthone (for example, KAYACURE DETX-S, produced by Nippon Kayaku Co., Ltd.), an aromatic ketone compound, for example, Michler's ketone, and a heterocyclic compound, for example, N-aryloxazolidinone.
Other examples include compounds described in European Patent 568,993, U.S. Patents 4,508,811 and 5,227,227, JP-A-2001 -125255 and JP-A-11-271969.
The infrared ray shielding composition according to the invention may or may not contain the sensitizer, and in the case of containing the sensitizer, the content thereof is preferably from 0.01 to 10% by weight, more preferably from 0.1 to 2% by weight, based on the total solid content of the infrared ray shielding composition according to the invention.
[9] Crosslinking Agent
The infrared ray shielding composition according to the invention may further contain a crosslinking agent for the purpose of increasing the strength of the infrared ray shielding film.
As to the crosslinking agent, a compound having a crosslinkable group is preferred, and a compound having two or more crosslinkable groups is more preferred. Specific examples of the crosslinkable group suitably include an oxetane group, a cyanate group and those groups described for the crosslinkable group which the alkali-soluble binder may have. Among them, an epoxy group, an oxetane group and a cyanate group are preferred. Specifically, the crosslinking agent is particularly preferably an epoxy compound, an oxetane compound or a cyanate compound.
Examples of the epoxy compound which can be suitably used as the crosslinking agent in the invention include an epoxy compound containing at least two oxirane groups per molecule and an epoxy compound having an alkyl group at the β-position and containing at least two epoxy groups per molecule.
Examples of the epoxy compound having at least two oxirane groups per molecule include a bixylenol-type or biphenol-type epoxy compound (for example, YX4000 produced by Japan Epoxy Resin Co., Ltd.) or a mixture thereof, a heterocyclic epoxy compound having an isocyanurate skeleton or the like (for example, TEPIC produced by Nissan Chemical Industries, Ltd. and ARALDITE PT810 produced by BASF Japan Ltd.), a bisphenol A-type epoxy compound, a novolac-type epoxy compound, a bisphenol F-type epoxy compound, a hydrogenated bisphenol A-type epoxy compound, a bisphenol S-type epoxy compound, a phenol novolac-type epoxy compound, a cresol novolac-type epoxy compound, a halogenated epoxy compound (for example, low-brominated epoxy compound, high-halogenated epoxy compound or brominated phenol novolac-type epoxy compound), an allyl group-containing bisphenol A-type epoxy compound, a trisphenolmethane-type epoxy compound, a diphenyldimethanol-type epoxy compound, a phenol-biphenylene-type epoxy compound, a dicyclopentadiene-type epoxy compound (for example, HP-7200 and HP-7200H produced by Dainippon Ink and Chemicals, Inc.), a glycidylamine-type epoxy compound (for example, diarninodiphenylmethane-type epoxy compound, glycidylaniline or triglycidylaminophenol), a glycidylester-type epoxy compound (for example, diglycidyl phthalate, diglycidyl adipate, diglycidyl hexahydrophthalate or diglycidyl dimerate), a hydantoin-type epoxy compound, an alicyclic epoxy compound (for example,
3,4-epoxycyclohexylmethyl-3 ',4'-epoxycyclohexane carboxylate,
bis(3,4-epoxycyclohexylmethyl)adipate, dicyclopentadiene diepoxide or GT-300, GT-400 and ZEHPE 3150 produced by Daicel Corp.), an imide alicyclic epoxy compound, a trihydroxyphenylmethane-type epoxy compound, a bisphenol A novolac-type epoxy compound, a tetraphenylolethane-type epoxy compound, a glycidyl phthalate compound, a tetraglycidyl xylenoylethane compound, a naphthalene group-containing epoxy compound (for example, naphthol aralkyl-type epoxy compound, naphthol novolac-type epoxy compound or tetrafunctional naphthalene-type epoxy compound and as a commercially available product, ESN- 190 and ESN-360 produced by Nippon Steel Chemical Co., Ltd. or HP-4032, EXA-4750 and EXA-4700 produced by Dainippon Ink and Chemicals, Inc.), a reaction product of epichlorohydrin and a polyphenol compound which is obtained by addition reaction between a phenol compound and a diolefm compound, for example, divinylbenzene and dicyclopentadiene, an epoxidation product of a ring-opening polymerization product of 4-vinylcyclohexene-l-oxide compound with peracetic acid or the like, an epoxy compound having a linear phosphorus-containing structure, an epoxy compound having a cyclic phosphorus-containing structure, an a-methylstilbene-type liquid crystal epoxy compound, a dibenzoyloxybenzene-type liquid crystal epoxy compound, an azophenyl-type liquid crystal epoxy compound, an azomethine phenyl-type liquid crystal epoxy compound, a binaphthyl-type liquid crystal epoxy compound, an azine-type epoxy compound, a glycidyl methacrylate copolymer-based epoxy compound (for example, CP-50S and CP-50M produced by NOF Corp.), a copolymer epoxy compound of cyclohexylmaleimide and glycidyl methacrylate, a bis(glycidyloxyphenyl)fluorene-type epoxy compound and a bis(glycidyloxyphenyl)adamantane-type epoxy compound, but the invention should not be construed as being limited thereto. The epoxy resins may be used individually or in combination of two or more thereof.
Other than the epoxy compound containing at least two oxirane groups per molecule, an epoxy compound having an alkyl group at the β-position and containing at least two epoxy groups per molecule can be used. A compound containing an epoxy group substituted with an alkyl group at the β-position (more specifically, a β-alkyl-substituted glycidyl group or the like) is particularly preferred.
In the epoxy compounds containing at least an epoxy group having an alkyl group at the β-position, all of two or more epoxy groups contained per molecule may be a β-alkyl-substituted glycidyl group or at least one epoxy group may be a β-alkyl-substituted glycidyl group.
Examples of the oxetane compound include an oxetane resin having at least two oxetanyl groups per molecule.
Specific examples thereof include polyfunctional oxetane, for example,
bis[(3-methyl-3-oxetanylmethoxy)methyl]ether, bis[(3-ethyl-3-oxetanylmethoxy)methyl]ether, 1 ,4-bis[(3-methyl-3-oxetanylmethoxy)methyl]benzene,
1 ,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, (3-methyl-3-oxetanyl)methyl acrylate, (3-ethyl-3-oxetanyl)methyl acrylate, (3-methyl-3-oxetanyl)methyl methacrylate,
(3-ethyl-3-oxetanyl)methyl methacrylate, or an oligomer or copolymer thereof; and an ether compound of a compound having an oxetane group and a compound having a hydroxy group, for example, a novolac resin, poly(p-hydroxystyrene), a cardo-type bisphenol, a calixarene, a
calixresorcinarene or silsesquioxane. Other examples include a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth)acrylate.
Examples of the bismaleimide compound include 4,4'-diphenylmethanebismaleimide, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane and 2,2'-bis[4-(4-maleimidophenoxy)phenyl]propane.
Examples of the cyanate compound include a bis A-type cyanate compound, a bis F-type cyanate compound, a cresol novolac-type cyanate compound and a phenol novolac-type cyanate compound.
As the crosslinking agent, melamine or a melamine derivative can be used.
Examples of the melamine derivative include methylolmelamine and an alkylated methylolmelamine (a compound obtained by etherifying a methylol group with methyl, ethyl, butyl or the like).
The crosslinking agents may be used individually or in combination of two or more thereof. The crosslinking agent is preferably melamine or an alkylated memylolmelarnine, more preferably a hexamethylated methylolmelamine, because they have good preservation stability and are effective in increasing the surface hardness of the photosensitive layer or the film strength of the infrared ray shielding film (cured film) itself.
The infrared ray shielding composition according to the invention may or may not contain the crosslinking agent, and in the case of containing the crosslinking agent, the content thereof is preferably from 1 to 40% by weight, more preferably from 3 to 20% weight, based on the total solid content of the infrared ray shielding composition according to the invention.
[10] Curing Accelerator
The infrared ray shielding composition according to the invention may further contain a curing accelerator for the purpose of accelerating heat curing of the crosslinking agent, for example, an epoxy compound or an oxetane compound.
Examples of the curing accelerator which can be used include an amine compound (for example, dicyandiamide, benzyldimethylamine, 4-(dimemylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine or 4-methyl-N,N-dimethylbenzylamine), a quaternary ammonium salt compound (for example, triethylbenzylammonium chloride), a blocked isocyanate compound (for example, dimethylamine), an imidazole derivative dicyclic amidine compound or salt thereof (for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, l-cyanoethyl-2-phenylimidazole or 1- (2-cyanoethyl)-2-ethyl-4-methylimidazole), a phosphorus compound (for example,
triphenylphosphine), a guanamine compound (for example, melamine, guanamine, acetoguan amine or benzoguanamine), and an S-triazine derivative (for example,
2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine,
2-vinyl-4,6-diarnino-S-triazine-isocyanuric acid adduct or
2,4-diamino-6-methacryloyloxyethyl-S-triazine-isocyanuric acid adduct). The curing accelerator is preferably melamine or dicyandiamide.
The curing accelerators may be used individually or in combination of two or more thereof. The infrared ray shielding composition according to the invention may or may not contain the curing accelerator, and in the case of containing the curing accelerator, the content thereof is preferably from 0.01 to 15% by weight based on the total solid content of the infrared ray shielding composition according to the invention.
[11] Filler
The infrared ray shielding composition according to the invention may further contain a filler. The filler which can be used in the invention includes a spherical silica surface-treated with a silane coupling agent.
The infrared ray shielding composition containing a filler according to the invention is preferred because an infrared ray shielding film having high durability can be obtained (in particular, this effect is remarkable when more severe durability is required of a solder resist, for example, in the case where a metal wiring covered with a solder resist has a high wiring density).
By using the spherical silica surface-treated with a silane coupling agent, the thermal cycle test resistance and preservation stability of the infrared ray shielding composition is increased and, for example, even after passing through a sever atmosphere, for example, the thermal cycle test, the same good profile as that immediately after pattern formation can be maintained.
The "spherical" as to the spherical filler is sufficient if the particle is not in an acicular, columnar or amorphous shape but is rounded, and the particle need not be necessarily "perfectly spherical", but a typical "spherical" shape is a "perfectly spherical" shape.
Whether the filler is spherical can be confirmed by observation through a scanning electron microscope (SEM).
The volume average particle size of the primary particle of the filler is not particularly restricted and may be appropriately selected according to the purpose, and is preferably from 0.05 to 3 um, and more preferably from 0.1 to 1 um. When the average particle size of the primary particle of the filler is in the range described above, reduction in the processability due to development of thixotropy is suppressed and increase in the maximum particle size is prevented, which is advantageous in that the generation of defect caused by attachment of a foreign material to the infrared ray shielding film (cured film) formed or unevenness of the coated layer is prevented.
The volume average particle size of the primary particle of the filler can be measured by a dynamic light scattering particle size distribution measuring device.
The filler can be dispersed by using the dispersing agent or binder described above. As described above, the alkali-soluble binder polymer having a crosslinkable group in the side chain is particularly preferred from the standpoint of curability.
-Surface treatment-
The surface treatment of the filler is described below. The surface treatment of the filler is not particularly restricted and may be appropriately selected according to the purpose, and a treatment of covering silica with a silane coupling agent is preferred.
-Silane coupling agent-
The silane coupling agent used for the surface treatment of the filler is not particularly restricted and may be appropriately selected according to the purpose, and it preferably has at least one functional group selected from an alkoxysilyl group, a chlorosilyl group and an acetoxysilyl group (hereinafter, also referred to as a "first functional group" sometimes) and at least one functional group selected from a (meth)acryloyl group, an amino group and an epoxy group (hereinafter, also referred to as a "second functional group" sometimes). The second functional group is more preferably a (meth)acryloyl group or an amino group, and still more preferably a (meth)acryloyl group. It is advantageous from the standpoint of preservation stability and TCT resistance that the second functional group is a (meth)acryloyl group.
A silane coupling agent described in JP-B-7-68256 containing as the first functional group, at least one group selected from an alkoxysilyl group, a chlorosilyl group and an acetoxysilyl group, and as the second functional group, at least one group selected from an imidazole group, an alkylimidazole group and a vinyl imidazole group is also preferably used.
The silane coupling agent is not particularly restricted and suitable examples thereof include γ-aminopropyltriethoxysilane, N-(p-ammoemyl)-y-aminopropyltrimethoxysilane,
N-(P-ammoethyl)-Y-aminopropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-memaciyloxypropyltrimethoxysilane,
γ-methacryloxypropylmethyldimethoxysilane, and
a-[[3-(trimethoxysilyl)propoxy]memyl]-imidazole-l-ethanol,
2-ethyl-4-methyl-a- [[3 -(trimethoxysilyl)propoxy]methyl] -imidazole- 1 -ethanol,
4-vinyl-a-[[3-(1rimethoxysilyl)propoxy]methyl]-iraidazole- 1 -ethanol,
2-ethyl-4-methylimidazopropyl1rimethoxysilane and salts, intramolecular condensates and intermolecular condensates thereof described in JP-B-7-68256, and as a commercially available product, KBM-503 (produced by Shin-Etsu Silicone Co., Ltd.). The silane coupling agents may be used individually or in combination of two or more thereof.
The surface treatment of the spherical silica with the silane coupling agent may be previously performed for only the spherical silica (in this case, hereinafter, the treatment is also referred to as a "pretreatment" sometimes) or may be performed together with a part or all of other fillers contained in the infrared ray shielding composition.
The method for performing the pretreatment is not particularly restricted and examples thereof include a dry method, an aqueous solution method, an organic solvent method and a spraying method. The temperature for performing the pretreatment is not particularly restricted and is preferably from ordinary temperature to 200°C.
At the pretreatment, it is also preferred to add a catalyst. The catalyst is not particularly restricted and examples thereof include an acid, a base, a metal compound and an organic metal compound.
The amount of the silane coupling agent added when performing the pretreatment is not particularly restricted and is preferably from 0.01 to 50 parts by weight, more preferably from 0.05 to 50 parts by weight, per 100 parts by weight of the spherical silica. When the amount is in the range described above, the surface treatment sufficient for exhibiting the effect is performed and reduction in the handling property resulting from aggregation of the spherical silica after treatment is suppressed.
The silane coupling agent has an action of increasing the adhesion property between the substrate and the photosensitive layer, because the first functional group reacts with an active group on the substrate surface, on the spherical silica surface or in the binder, and further the second functional group reacts with a carboxyl group or an ethylenically unsaturated group in the binder. On the other hand, the silane coupling agent has high reactivity and therefore, when the silane coupling agent itself is added to the infrared ray shielding composition, due to its diffusing action, mainly the second functional group is reacted or deactivated during preservation to cause decrease in shelf life or pot life in some cases.
However, when the spherical silica which is pretreated with a silane coupling agent as described above is used, since the diffusing action is suppressed, the problem in the shelf life or pot life is greatly improved and it is possible to make a one-component type composition. Moreover, in the case of applying the pretreatment to the spherical silica, since the conditions, for example, stirring condition, temperature condition or use of a catalyst can be feely selected, the reaction rate between the first functional group of the silane coupling agent and the active group of the spherical silica can be significantly increased in comparison with the case of adding the spherical silica without performing the pretreatment. Therefore, very good results can be obtained particularly in severe characteristics required, for example, electroless gold plating, electroless solder plating and humidity resistance load test. Also, by performing the pretreatment, the amount of the silane coupling agent used can be reduced and the shelf life and pot life can be more improved.
Examples of the spherical silica surface-treated with a silane coupling agent for use in the invention include FB and SFP Series of Denki Kagaku Kogyo Kabushiki Kaisha, 1-FX of Tatsumori Ltd., HSP Series of Toagosei Co., Ltd., and SP Series of Fuso Chemical Co., Ltd.
The infrared ray shielding composition according to the invention may or may not contain the filler and in the case of containing the filler, although the content of the filler is not particularly restricted and may be appropriately selected according to the purpose, it is preferably from 1 to 60% by weight based on the total solid content of the infrared ray shielding composition. When the content is in the range described above, a sufficient reduction in the linear expansion coefficient is achieved and the infrared ray shielding film (cured film) formed is prevented from embrittlement and thus, its function as a protective film of wiring is sufficiently exerted when the wiring is formed using the infrared ray shielding film.
[12] Elastomer
The infrared ray shielding composition according to the invention may further contain an elastomer.
By incorporating the elastomer, when the infrared ray shielding composition is used for a solder resist, the adhesion property to a conductive layer of a printed wiring board can be more increased and the heat resistance, heat shock resistance, flexibility and toughness of the infrared ray shielding film (cured film) can be more increased.
The elastomer which can be used in the invention is not particularly restricted and may be appropriately selected according to the purpose. Examples thereof include a styrene-based elastomer, an olefin-based elastomer, a urethane-based elastomer, a polyester-based elastomer, a polyamide-based elastomer, an acrylic elastomer and a silicone-based elastomer. The elastomer is composed of a hard segment component and a soft segment component, where ordinarily, the former contributes to the heat resistance and strength and the latter contributes to the flexibility and toughness. Of the elastomers, a polyester-based elastomer is advantageous in view of compatibility with other materials.
Examples of the styrene-based elastomer include a styrene-butadiene-styrene block copolymer, a styrene-isoprene-styrene block copolymer, a styrene-ethylene-butylene-styrene block copolymer and a styrene-ethylene-propylene-styrene block copolymer. As the component constituting the styrene-based elastomer, other than styrene, a styrene derivative, for example, a-methylstyrene, 3-methylstyrene, 4-propylstyrene or 4-cyclohexylstyrene can be used. Specific examples thereof include TUFPRENE, SOLPRENE T, ASAPRENE T and TUFTEC (produced by Asahi Chemical Industry Co., Ltd.), ELASTOMER AR (produced by Aronkasei Co., Ltd.), KRATON G and CALIFLEX (produced by Shell Chemicals Japan Ltd.), JSR-TR, TSR-SIS and DYNARON (produced by JSR Corp.), DENKA STR (produced by Denki Kagaku Kogyo Kabushiki Kaisha), QUINTAC (produced by ZEON Corp.), TPE-SB Series (produced by Sumitomo Chemical Co., Ltd.), RABALON (produced by Mitsubishi Chemical Corp.), SEPTON and HYBRAR (produced by Kuraray Co., Ltd.), SUMIFLEX (produced by Sumitomo Bakelite Co., Ltd.), LEOSTOMER and ACTYMER (produced by Riken Vinyl Industry Co., Ltd.).
The olefin-based elastomer is a copolymer of an a-olefin having from 2 to 20 carbon atoms, for example, ethylene, propylene, 1-butene, 1-hexene or 4-methylpentene, and examples thereof include an ethylene-propylene copolymer (EPR) and an ethylene-propylene-diene copolymer (EPDM). Other examples of the olefin-based elastomer include a copolymer of an a-olefin and a non-conjugated diene having from 2 to 20 carbon atoms, for example, dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylenenorbornene, ethylidenenorbornene, butadiene or isoprene, and an epoxidized polybutadiene. The olefin-based elastomer further includes, for example, a carboxyl-modified NBR obtained by copolymerizing a methacrylic acid with a butadiene-acrylonitrile copolymer. In addition, the olefin-based elastomer includes, for example, an ethylene-a-olefin copolymer rubber, an ethylene-a-olefin-non-conjugated diene copolymer rubber, a propylene-a-olefin copolymer rubber and a butene-a-olefin copolymer rubber.
Specific examples of the olefin-based elastomer include MILASTOMER (produced by Mitsui Petrochemical Industries, Ltd.), EXACT (produced by Exxon Chemical Corp.), ENGAGE (produced by Dow Chemical Co.), hydrogenated styrene-butadiene rubber (DYNABON HSBR, produced by JSR Corp.), butadiene-acrylonitrile copolymer (NBR Series, produced by JSR Corp.), crosslinking point-containing butadiene-acrylonitrile copolymer modified with carboxyl group at both terminals (XER Series, produced by JSR Corp.) and epoxidized polybutadiene in which polybutadiene is partially epoxidized (BF- 1000, produced by Nippon Soda Co., Ltd.).
The urethane-based elastomer comprises a hard segment composed of a low molecular (short chain) diol and a diisocyanate and a soft segment composed of a high molecular (long chain) diol and a diisocyanate. Examples of the high molecular (long chain) diol include polypropylene glycol, polytetramethylene oxide, poly(l,4-butylene adipate), poly(ethylene-l,4-butylene adipate), polycaprolactone, poly(l,6-hexylene carbonate) and poly(l,6-hexylene-neopentylene adipate). The number average molecular weight of the high molecular (long chain) diol is preferably from 500 to 10,000. Examples of the low molecular (short chain) diol include ethylene glycol, propylene glycol, 1,4-butanediol and bisphenol A. The number average molecular weight of the short chain diol is preferably from 48 to 500. Specific examples of the urethane-based elastomer include PANDEX T-2185 and T-2983N (produced by Dainippon Ink and Chemicals, Inc.) and MIRACTRAN E790.
The polyester-based elastomer is obtained by polycondensing a dicarboxylic acid or a derivative thereof and a diol compound or a derivative thereof. Specific examples of the dicarboxylic acid include an aromatic dicarboxylic acid, for example, terephthalic acid, isophthalic acid or naphthalenedicarboxylic acid, an aromatic dicarboxylic acid formed by substituting for a hydrogen atom of the aromatic ring of the dicarboxylic acid above with a methyl group, an ethyl group, a phenyl group or the like, an aliphatic dicarboxylic acid having from 2 to 20 carbon atoms, for example, adipic acid, sebacic acid or dodecanedicarboxylic acid, and an alicyclic dicarboxylic acid, for example, cyclohexanedicarboxylic acid. The dicarboxylic acids may be used individually or in combination of two or more thereof. Specific examples of the diol compound include an aliphatic diol and an alicyclic diol, for example, ethylene glycol, 1 ,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol or 1,4-cyclohexanediol, bisphenol A, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-3-methylphenyl)propane and resorcin. The diol compounds may be used individually or in combination of two or more thereof. Also, a multi-block copolymer having an aromatic polyester (for example, polybutylene terephthalate) moiety as the hard segment component and an aliphatic polyester (for example, polytetramethylene glycol) moiety as the soft segment component may be used. There are polyester elastomers of various grades according to the kind, ratio, molecular weight difference or the like of the hard segment and soft segment. Specific examples of the polyester-based elastomer include HYTREL (produced by Du Pont-Toray Co., Ltd.), PELPRENE (produced by Toyobo Co., Ltd.) and ESPEL (produced by Hitachi Chemical Co., Ltd.).
The polyamide-based elastomer comprises a hard segment composed of polyamide and a soft segment composed of polyether or polyester and is roughly classified into two types of a polyether block amide type and a polyether-ester block amide type. Examples of the polyamide include polyamide 6, polyamide 11 and polyamide 12. Examples of the polyether include polyoxyethylene, polyoxypropylene and polytetramethylene glycol. Specific examples of the polyamide-based elastomer include UBE Polyamide Elastomer (produced by Ube Industries, Ltd.), DAIAMIDE (produced by Daicel-Huels Ltd.), PEBAX (produced by Toray Industries, Inc.), GRILON ELY (EMS-CHEMIE (Japan) Ltd.), NOVAMID (produced by Mitsubishi Chemical Corp.) and GRILAX (produced by Dainippon Ink and Chemicals, Inc.).
The acrylic elastomer is obtained by copolymerizing an acrylic acid ester, for example, ethyl acrylate, butyl acrylate, methoxyethyl acrylate or ethoxyethyl acrylate with an epoxy group-containing monomer, for example, glycidyl methacrylate or alkyl glycidyl ether and/or a vinyl monomer, for example, acrylonitrile or ethylene. Examples of the acrylic elastomer include an acrylonitrile-butyl acrylate copolymer, an acrylonitrile-butyl acrylate-ethyl acrylate copolymer and an acrylonitrile-butyl acrylate-glycidyl methacrylate copolymer.
The silicone-based elastomer is mainly composed of an organopolysiloxane and classified into a polydimethylsiloxane type, a polymethylphenylsiloxane type and a polydiphenylsiloxane type. An organopolysiloxane partially modified with a vinyl group, an alkoxy group or the like may also be used. Specific examples of the silicone-based elastomer include KE Series (produced by Shin-Etsu Chemical Co., Ltd.), SE Series, CY Series and SH Series (produced by Dow Corning Toray Silicone Co., Ltd.).
Other than the elastomers described above, a rubber-modified epoxy resin can be used. The rubber-modified epoxy resin is obtained by modifying a part or all of epoxy groups of, for example, the bisphenol F-type epoxy resin, bisphenol A-type epoxy resin, salicylaldehyde-type epoxy resin, phenol novolac-type epoxy resin or cresol novolac-type epoxy resin described above, with both-terminal carboxyl group-modified butadiene-acrylonitrile rubber, terminal amino-modified silicone rubber or the like.
Of the elastomers, from the standpoint of shear adhesion property and heat shock resistance, a butadiene-acrylonitrile copolymer modified with carboxyl group at both terminals, a polyester-based elastomer having a hydroxy group (ESPEL 1612 and 1620, produced by Hitachi Chemical Co., Ltd.) and an epoxidized polybutadiene are preferred.
The infrared ray shielding composition according to the invention may or may not contain the elastomer and in the case of containing the elastomer, although the content of the elastomer is not particularly restricted and may be appropriately selected according to the purpose, it is preferably from 0.5 to 30% by weight, more preferably from 1 to 10% by weight, particularly preferably from 3 to 8% by weight, based on the total solid content of the infrared ray shielding composition. It is advantageous that the content is in the preferred range described above because the shear adhesion property and heat shock resistance can be more improved.
[13] Surfactant
To the infrared ray shielding composition according to the invention may be added various surfactants from the standpoint of more improving the coating property. As the surfactant, various surfactants, for example, a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant or a silicone-based surfactant may be used.
In particular, by incorporating a fluorine-based surfactant into the infrared ray shielding composition according to the invention, the liquid property (particularly, fluidity) of a coating solution prepared from the infrared ray shielding composition can be more improved so that uniformity of the coating thickness and liquid saving property can be more improved.
Specifically, in the case of forming a layer using a coating solution prepared from the infrared ray shielding composition containing a fluorine-based surfactant, the interfacial tension between the coating surface and the coating solution is reduced, whereby wettability of the coating surface is increased and the coating property onto the coating surface is improved. Therefore, even when a thin layer of approximately several μηι is formed using a smaller amount of the coating solution, it is effective from the standpoint that a layer having a uniform thickness with small unevenness in thickness is suitably formed.
The fluorine content in the fluorine-based surfactant is preferably from 3 to 40% by weight, more preferably from 5 to 30% by weight, and particularly preferably from 7 to 25% by weight. The fluorine-based surfactant having the fluorine content of the range described above is effective in view of the uniformity of the coating thickness and liquid saving property and also exhibits good solubility in the infrared ray shielding composition.
Examples of the fluorine-based surfactant include MEGAFAC F171, MEGAFAC F172, MEGAFAC F173, MEGAFAC F176, MEGAFAC F177, MEGAFAC F141, MEGAFAC F142, MEGAFAC F143, MEGAFAC F144, MEGAFAC R30, MEGAFAC F437, MEGAFAC F475, MEGAFAC F479, MEGAFAC F482, MEGAFAC F554, MEGAFAC F780 and MEGAFAC F781 (produced by DIC Corp.), FLUORAD FC430, FLUORAD FC431 and FLUORAD FC171 (produced by Sumitomo 3M Ltd.), and SURFLON S-382, SURFLON SC-101, SURFLON SC-103, SURFLON SC-104, SURFLON SC-105, SURFLON SC-1068, SURFLON SC-381 , SURFLON SC-383, SURFLON S-393 and SURFLON KH-40 (produced by Asahi Glass Co., Ltd.).
Specific examples of the nonionic surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate and a sorbitan fatty acid ester (for example, PLURONIC L10, L31, L61, L62, 10R5, 17R2 and 25R2 and TETRONIC 304, 701, 704, 901, 904 and 150R1 (produced by BASF) and SOLSPERSE 20000 (produced by Zeneca).
Specific examples of the cationic surfactant include a phmdocyanine derivative (EFKA-745, produced by Morishita Sangyo K.K.), Organosiloxane Polymer KP341 (produced by Shin-Etsu Chemical Co., Ltd.), a (meth)acrylic acid (co)polymer (POLYFLOW No. 75, No. 90 and No. 95 (produced by Kyoeisha Chemical Co., Ltd.), and W001 (produced by Yusho Co Ltd.).
Specific examples of the anionic surfactant include W004, W005 and W017 (produced by Yusho Co Ltd.).
Examples of the silicone-based surfactant include TORAY SILICONE DC3PA, TORAY SILICONE SH7PA, TORAY SILICONE DCllPA, TORAY SILICONE SH21PA, TORAY SILICONE SH28PA, TORAY SILICONE SH29PA, TORAY SILICONE SH30PA and TORAY SILICONE SH8400 (produced by Dow Corning Toray Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460 and TSF-4452 (produced by Momentive Performance Materials Inc.), KP341, KF6001 and KF6002 (produced by Shin-Etsu Silicone Co., Ltd.), and BYK-323 and BYK-330 (produced by Byk-Chemie GmbH).
The surfactants may be used individually or in combination of two or more thereof.
The infrared ray shielding composition according to the invention may or may not contain the surfactant, and in the case of containing the surfactant, the content thereof is preferably from 0.001 to 1% by weight, more preferably from 0.01 to 0.1% by weight, based on the total solid content of the infrared ray shielding composition according to the invention.
[1 ] Other Components
In addition to the essential components and preferred additives described above, other components may be appropriately selected and used according to the purpose in the infrared ray shielding composition according to the invention as long as the effects of the invention are not impaired.
Examples of other components which can be used include a heat curing accelerator, a thermal polymerization inhibitor, a plasticizer and a coloring agent (coloring pigment or dye). Further, an adhesion accelerator to the surface of base material, and other auxiliary agents (for example, an electrically conductive particle, a filler, a defoaming agent, a flame retardant, a leveling agent, a release accelerator, an antioxidant, a perfume, a surface tension-controlling agent or a chain transfer agent) may be used in combination.
By appropriately incorporating such a component into the infrared ray shielding composition, the properties of the intended solder resist, for example, stability, photographic property or physical property of film can be adjusted.
Details of the thermal polymerization inhibitor are described, for example, in paragraphs [0101] and [0102] of JP-A-2008-250074.
Details of the plasticizer are described, for example, in paragraphs [0103] and [0104] of JP-A-2008-250074.
Details of the coloring agent are described are described, for example, in paragraphs [0105] and [0106] of JP-A-2008-250074 and paragraphs [0038] and [0039] of JP-A-2009-205029.
Details of the adhesion accelerator are described, for example, in paragraphs [0107] to [0109] of JP-A-2008-250074.
Any of the additives described in the patent documents above is usable in the infrared ray shielding composition according to the invention.
In the infrared ray shielding composition according to the invention, the solid content concentration is preferably from 5 to 90% by weight, more preferably from 20 to 80% by weight, and most preferably from 40 to 60% by weight.
The use of the infrared ray shielding composition according to the invention is not particularly restricted and examples thereof include a solder resist, an infrared ray shielding film for the back surface of a silicon substrate in a solid-stage imaging device (infrared ray shielding solder resist in a solid-stage imaging device), and an infrared ray shielding film for a waver level lens. The infrared ray shielding composition according to the invention is preferably used for a solder resist or an infrared ray shielding film for the back surface of a silicon substrate in a solid-stage imaging device (infrared ray shielding solder resist in a solid-stage imaging device).
In the case where the infrared ray shielding composition according to the invention is used for a solder resist or an infrared ray shielding film for the back surface of a silicon substrate in a solid-stage imaging device (infrared ray shielding solder resist in a solid-stage imaging device), in order to form a coating film having a relatively large thickness, the solid content concentration is preferably from 30 to 80% by weight, more preferably from 35 to 70% by weight, and most preferably from 40 to 60% by weight.
Also, the viscosity of the infrared ray shielding composition according to the invention is preferably in a range from 1 to 3,000 mPa-s, more preferably in a range from 10 to 2,000 mPa s, and most preferably in a range from 100 to 1,500 mPa s.
In the case where the infrared ray shielding composition according to the invention is used for a solder resist or an infrared ray shielding film for the back surface of a silicon substrate in a solid-stage imaging device (infrared ray shielding solder resist in a solid-stage imaging device), the viscosity is preferably in a range from 10 to 3,000 mPa-s, more preferably in a range from 500 to 1,500 mPa-s, most preferably in a range from 700 to 1,400 mPa-s, from the standpoint of thick film-forming property and uniform coating property.
The invention also relates to a photosensitive layer formed from the infrared ray shielding composition according to the invention. Since the photosensitive layer is formed of the infrared ray shielding composition according to the invention, the photosensitive layer has a high light shielding property in the infrared region and high light transparency in the visible region and is capable of forming an infrared ray shielding film in which the occurrence of cracking is restrained and which exhibits a high adhesion property to a substrate and high exposure sensitivity. Further, by incorporating an alkali-soluble binder into the infrared ray shielding composition according to the invention, a pattern having the desired profile of high rectangularity can be formed through exposure and alkali development.
Moreover, the invention relates to an infrared ray shielding film which is a cured film formed from the infrared ray shielding composition according to the invention. The infrared ray shielding film according to the invention is a cured film which has a high light shielding property in the infrared region and high light transparency in the visible region, in which the occurrence of cracking is restrained and which exhibits a high adhesion property to a substrate and high exposure sensitivity. Further, when the photosensitive layer formed by incorporating an alkali-soluble binder into the infrared ray shielding composition according to the invention is subjected to exposure and alkali development, the infrared ray shielding film according to the invention including a pattern having the desired profile of high rectangularity can be formed.
Furthermore, the invention also relates to a pattern forming method comprising, in this order, a step of forming a photosensitive layer using the infrared ray shielding composition according to the invention, a step of pattern-exposing the photosensitive layer to cure the exposed area, and a step of removing the unexposed area by alkali development to form a pattern.
The pattern forming method is described in detail below by taking, as an example, a patterned solder resist formed using the infrared ray shielding composition according to the invention. However, the descriptions relating to the kind and amount of solvent for preparation of a coating solution, the coating method of the coating solution, the thickness of the photosensitive layer, and the exposure step and other steps are not restricted to the solder resist. Now, a case of forming a photosensitive layer (polymerizable composition layer) using the infrared ray shielding composition is described as an example.
-Photosensitive Layer-
For forming a patterned solder resist (solder resist pattern), first, a photosensitive layer is formed using the infrared ray shielding composition according to the invention. The photosensitive layer is not particularly restricted as long as it is a layer formed from the infrared ray shielding composition. The layer thickness, stack structure and the like can be appropriate selected according to the purpose.
The method for forming the photosensitive layer includes a method of dissolving, emulsifying or dispersing the infrared ray shielding composition according to the invention in water or a solvent to prepare a coating solution, coating the coating solution directly and drying the coating.
The solvent for the preparation of the coating solution included in the infrared ray shielding composition according to the invention is not particularly restricted and a solvent capable of uniformly dissolving or dispersing each component of the infrared ray shielding composition according to the invention may be appropriately selected according to the purpose. Examples thereof include an alcohol, for example, methanol, ethanol, normal propanol, isopropanol, normal butanol, secondary butanol or normal hexanol, a ketone, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisobutyl ketone, cyclohexanone or cyclopentanone, an ester, for example, ethyl acetate, butyl acetate, normal amyl acetate, methyl sulfate, ethyl propionate, dimethyl phthalate, ethyl benzoate, propylene glycol monomethyl ether acetate (PGMEA, also known as l-methoxy-2-acetoxypropane) or methoxypropyl acetate, an aromatic hydrocarbon, for example, toluene, xylene, benzene or ethylbenzene, a halogenated hydrocarbon, for example, carbon tetrachloride, trichloroethylene, chloroform, 1,1,1-trichloroethane, methylene chloride or monochlorobenzene, an ether, for example, tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, l-methoxy-2-propanol or propylene glycol monomethyl ether (PGME, also known as l-methoxy-2-propanol), dimethylformarnide, dimethylacetamide, dimethylsulfoxide, and sulfolane. The solvents may be used individually or in combination of two or more thereof. Also, a known surfactant may be added.
Propylene glycol monomethyl ether acetate (PGMEA) is preferred from the standpoint of uniform dissolution or dispersion of each component of the infrared ray shielding composition according to the invention.
The method of coating the coating solution on a support is not particularly restricted and may be appropriately selected according to the purpose, and examples thereof include a method of coating the coating solution using a spin coater, a slit spin coater, a roll coater, a die coater or a curtain coater.
The drying conditions of the coating layer may vary depending on the respective components, the kind of solvent, the amount used and the like, and the drying is ordinarily conducted at temperature approximately from 60 to 150°C for approximately from 30 seconds to 15 minutes.
The thickness of the photosensitive layer is not particularly restricted and may be appropriately selected according to the purpose, and is, for example, preferably from 1 to 100 urn, more preferably from 2 to 50 um, and particularly preferably from 4 to 30 um.
(Solder resist pattern forming method)
The method of forming a solder resist pattern using the infrared ray shielding composition according to the invention comprises at least an exposure step, and ordinarily further comprises a developing step in which the conditions are appropriately selected, if desired, and other steps. The term "exposure" as used in the invention includes not only exposure to light having various wavelengths but also irradiation with radiation, for example, an electron beam or an X-ray.
<Exposure step>
The exposure step is a step of exposing the photosensitive layer formed from the infrared ray shielding composition through a mask and in the step, only the region irradiated with light is cured.
The exposure is preferably performed by the irradiation with radiation and as the radiation usable at the exposure, an electron beam, KrF, ArF, an ultraviolet light, for example, g-line, h-line or i-line, or visible light is preferably used. In particular, KrF, g-line, h-line or i-line is preferred. Examples of the exposure system include stepper exposure and exposure with a high-pressure mercury lamp.
The exposure amount is preferably from 5 to 3,000 mJ/cm2, more preferably from 10 to 2,000 mJ/cm , and most preferably from 50 to 1,000 mJ/cm .
<Developing step>
Subsequent to the exposure step, an alkali development processing (developing step) is conducted to dissolve the area not irradiated with light in the exposure step, whereby only the photocured area remains and a patterned solder resist having infrared ray shielding property is formed.
The developer is preferably an organic alkali developer which does not cause damage on the underlying circuit or the like. The developing temperature is ordinarily from 20 to 40°C and the developing time is from 10 to 180 seconds.
As the alkali used for the developer, for example, an aqueous alkaline solution obtained by diluting an organic alkaline compound, for example, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine or l,8-diazabicyclo-[5,4,0]-7-undecene with pure water to have a concentration of ordinarily from 0.001 to 10% by weight, preferably from 0.01 to 1% by weight, is used. When a developer composed of such an aqueous alkaline solution is used, washing (rinsing) with pure water is ordinarily conducted after the development.
<Other steps>
Other steps are not particularly restricted and can be appropriately selected according to the purpose. Examples thereof include a surface treatment step of substrate, a curing treatment step and a post-exposure step.
<Curing treatment step>
The curing treatment step is a step of applying a curing treatment to the photosensitive layer having the pattern formed, if desired, after the developing step. By conducting the treatment, the mechanical strength of the infrared ray shielding film which is the cured film is enhanced.
The curing treatment step is not particularly restricted and may be appropriately selected according to the purpose, and suitable examples thereof include an entire surface exposing treatment and an entire surface heating treatment.
Examples of the method for the entire surface exposing treatment include a method where the entire surface of the stack having the patterned photosensitive layer formed is exposed after the developing step. BY the entire surface exposure, curing of the polymerization components in the infrared ray shielding composition forming the photosensitive layer is accelerated and curing of the infrared ray shielding film which is the cured film is further proceeds to improve the mechanical strength and durability.
The apparatus for conducting the entire surface exposure is not particularly restricted and may be appropriately selected according to the purpose, and preferred examples thereof include an UV exposing machine, for example, an ultrahigh-pressure mercury lamp.
Also, the method for the entire surface heating treatment includes a method where the entire surface of the stack having the patterned photosensitive layer formed is heated after the developing step. BY the entire surface heating, the film strength of the curing of the infrared ray shielding film which is the cured film is increased.
The heating temperature at the entire surface heating is preferably from 120 to 250°C, and more preferably from 140 to 250°C. When the heating temperature is 120°C or more, the film strength is increased by the heat treatment, and when the heating temperature is 250°C or less, the resin in the infrared ray shielding composition can be prevented from decomposing to weaken and embrittle the film quality.
The heating time in the entire surface heating is preferably from 3 to 180 minutes, and more preferably from 5 to 120 minutes.
The apparatus for conducting the entire surface heating is not particularly restricted and may be appropriately selected from known apparatuses according to the purpose, and examples thereof include a dry oven, a hot plate and an IR heater.
The patterned resist thus-formed has excellent infrared ray blocking property and thus, its application range is wide. Since the infrared ray shielding composition according to the invention is excellent in the light shielding property in the infrared region and light transparency in the ultraviolet to visible regions, a pattern having an excellent profile is formed and the infrared ray shielding film having the pattern formed has excellent infrared shielding property so that it is useful in the formation of a solder resist for a device with a photodiode having sensitivity to the infrared region, particularly, a solid-state imaging device.
As described above, the infrared ray shielding composition according to the invention is useful in the formation of not only a solder resist but also an infrared ray shielding film for the back surface of a silicon substrate in a solid-state imaging device or an infrared ray shielding film for a wafer-level lens.
Therefore, the invention also relates to a solid-state imaging device having an infrared ray shielding film formed from the infrared ray shielding composition according to the invention.
The solid-state imaging device according to an embodiment of the invention is described below with reference to Fig. 1 and Fig. 2, but the invention should not be construed as being limited thereto.
The portions common between Fig. 1 and Fig. 2 are indicated by a common reference numeral or sign.
Also, in the description, the terms "top", "above" and "upper side" each indicates a side farther from a silicon substrate 10, and the terms "bottom", "below" and "lower side" each indicates a side closer to the silicon substrate 10.
Fig. 1 is a schematic cross-sectional view showing a configuration of a camera module equipped with a solid-state imaging device according to a specific example of the embodiment above.
A camera module 200 shown in Fig. 1 is connected to a circuit substrate 70 as a mounting substrate through a solder ball 60 as a connection member.
More specifically, the camera module 200 is configured to comprise a solid-state imaging device substrate 100 having an image-forming device unit on a first major surface of a silicon substrate, a glass substrate 30 (light-transmitting substrate) disposed on the upper side of the first major surface of the solid-state imaging device substrate 100, an infrared cut filter 42 disposed above the glass substrate 30, a lens holder 50 having an imaging lens 40 and being disposed above the glass substrate 30 and the infrared cut filter 42, and a light-shielding and electromagnetic shield 44 disposed to surround the periphery of the solid-state imaging device substrate 100 and the glass substrate 30. Respective members are adhered using adhesives 20, 41, 43 and 45.
In the camera module 200, incident light hv from the outside sequentially passes through the imaging lens 40, the infrared cut filter 42 and the glass substrate 30 and reaches the imaging device unit of the solid-state imaging device substrate 100.
Also, the camera module 200 is connected to a circuit board 70 through a solder ball 60 (connection material) on the second major surface side of the solid-state imaging device substrate 100.
Fig. 2 is an enlarged cross-sectional view of the solid-state imaging device substrate 100 in
Fig. 1.
The solid-state imaging device substrate 100 is configured to comprise a silicon substrate 10 as a base material, an imaging device 12, an interlayer insulating film 13, a base layer 14, a red color filter 15R, a green color filter 15G, a blue color filter 15B, an overcoat 16, a microlens 17, a light shielding film 18, an insulating film 22, a metal electrode 23, a solder resist layer 24, an internal electrode 26 and a device surface electrode 27.
The solder resist layer 24 may be omitted.
First, the configuration on the first major surface side of the solid-state imaging device substrate 100 is mainly described below.
As shown in Fig. 2, an imaging device unit where a plurality of imaging devices 12, for example, CCD and CMOS are two-dimensionally arrayed is provided on the first major surface side of a silicon substrate 10 which is the base material of the solid-state imaging device substrate 100.
An interlayer insulating film 13 is formed on the imaging device 12 in the imaging device unit, and a base layer 14 is formed on the interlayer insulating film 13. Further, a red color filter 15R, a green color filter 15G and a blue color filter 15B (hereinafter, these are collectively referred to as a "color filter 15" sometimes) corresponding to respective imaging devices 12 are disposed on the base layer 14.
A light shielding film not shown may be provided in the boundaries of the red color filter 15R, the green color filter 15G and the blue color filter 15B and in the periphery of the imaging device unit. The light shielding film can be produced, for example, using a known black color resist.
An overcoat 16 is formed on the color filter 15, and a microlens 17 corresponding to the imaging device 12 (color filter 15) is formed on the overcoat 16.
In the periphery of the imaging device on the first major surface side, a peripheral circuit (not shown) and an internal electrode 26 are provided, and the internal electrode 26 is electrically connected to the imaging device 12 through the peripheral circuit.
Further, a device surface electrode 27 is formed on the internal electrode 26 through an interlayer insulating film 13. In the interlayer insulating film 13 between the internal electrode 26 and the device surface electrode 27, a contact plug (not shown) for electrically connecting these electrodes is formed. The device surface electrode 27 is used for voltage application and signal reading though the contact plug and the internal electrode 26.
A base layer 14 is formed on the device surface electrode 27. An overcoat 16 is formed on the base layer 14. The base layer 14 and the overcoat 16 formed on the device surface electrode 27 are opened to form a pad opening and to expose a part of the device surface electrode 27.
This is the configuration on the first major side of the solid-state imaging device substrate
100.
On the first major side of the solid-state imaging device substrate 100, an adhesive 20 is provided in the periphery of the imaging device part, and the solid-state imaging device substrate 100 and the glass substrate 30 are adhered through the adhesive 20.
The silicon substrate 10 has a through-hole penetrating the silicon substrate 10, and a penetrating electrode which is a part of the metal electrode 23 is provided in the through-hole. The imaging device unit and the circuit board 70 are electrically connected by the penetrating electrode. Next, the configuration on the second major surface side of the solid-state imaging device substrate 100 is mainly described below.
On the second major surface side, an insulating film 22 is formed from the second major surface to the inner wall of the through-hole.
On the insulating film 22, a metal electrode 23 patterned to extend from the region on the second major surface of the silicon substrate 10 to the inside of the through hole is provided. The metal electrode 23 is an electrode for connecting the imaging device unit in the solid-state imaging device substrate 100 and the circuit board 70.
The penetrating electrode is the portion formed inside the through hole of the metal electrode 23. The penetrating electrode penetrates the silicon substrate 10 and a part of the interlayer insulating film and reaches the lower side of the internal electrode 26 to be electrically connected to the internal electrode 26.
Also, on the second major surface side, a solder resist layer 24 (protective insulating film) covering the second major surface on which the metal electrode 23 is formed and having an opening to expose a part of the metal electrode 23 is provided.
Further, on the second major surface side, a light shielding film 18 covering the second major surface on which the solder resist layer 24 is formed and having an opening to expose a part of the metal electrode 23 is provided.
In this configuration, (1) an infrared ray shielding solder resist layer where the light shielding film 18 and the solder resist layer 24 together form a single layer may be formed from the infrared ray shielding composition according to the invention, or (2) the light shielding film 18 and the solder resist layer 24 are separate layers and the light shielding film 18 may be formed from the infrared ray shielding composition according to the invention (in this case, the solder resist layer may be formed using a known solder resist composition).
In Fig. 2, although the light shielding film 18 is patterned to cover a part of the metal electrode 23 and to expose the remaining portion, it may be patterned to expose the entirety of the metal electrode 23 (the same applies to the patterning of the solder resist layer 24).
Also, the solder resist layer 24 may be omitted and a light shielding film 18 may be formed directly on the second major surface where the metal electrode 23 is formed.
A solder ball 60 as a connection member is provided on the exposed metal electrode 23, and the metal electrode 23 of the solid-state imaging device substrate 100 and a connection electrode not shown of the circuit board 70 are electrically connected through the solder ball 60.
The configuration of the solid-state imaging device substrate 100 is described above, and each part other than the light shielding film 18 of the solid-state imaging device substrate 100 can be formed by a known method, for example, a method described in paragraphs [0033] to [0068] of JP-A-2009-158863 or a method described in paragraphs [0036] to [0065] of JP-A-2009-99591.
The light shielding film 18 can be formed by the method of producing the infrared ray shielding film according to the invention described above.
The interlayer insulating film 13 is formed as an Si02 film or an SiN film, for example, by sputtering or CVD (chemical vapor deposition).
The color filter 15 is formed, for example, by photolithography using a known color resist.
The overcoat 16 and the base layer 14 are formed, for example, by photolithography using a known resist for forming an organic interlayer film.
The microlens 17 is formed, for example, by photolithography using a styrene resin or the like.
In the case where the solder resist layer 24 and the light shielding film 18 are combined to form a single-layer infrared ray shielding solder resist layer, the layer is preferably formed using the infrared ray shielding composition according to the invention.
On the other hand, in the case where the solder resist layer 24 is a separate layer from the light shielding film 18, the solder resist layer 24 is preferably formed, for example, by photolithography using a known solder resist containing a phenolic resin, a polyimide resin or an amine resin.
The solder ball 60 is formed, for example, as Sn-Pb (eutectic), 95Pb-Sn (high-lead high melting point solder) or Pb-free solder by using Sn-Ag, Sn-Cu, Sn-Ag-Cu or the like. The solder ball 60 is formed, for example, as a sphere having a diameter from 100 to 1,000 um (preferably a diameter from 150 to 700 um).
The internal electrode 26 and the device surface electrode 27 are formed, for example, as a metal electrode, for example, Cu by CMP (chemical mechanical polishing) or photolithography and etching.
The metal electrode 23 is formed, for example, as a metal electrode, for example, Cu, Au, Al, Ni, W, Pt, Mo, Cu compound, W compound or Mo compound by sputtering, photolithography, etching or electrolytic plating. The metal electrode 23 may have a sing- layer configuration or a multilayer configuration consisting of two or more layers. The thickness of the metal electrode 23 is, for example, from 0.1 to 20 μιη (preferably from 0.1 to 10 um). The silicon substrate 10 is not particularly restricted and a silicon substrate thinned by grinding the back surface of the substrate may be used. The thickness of the substrate is not restricted and a silicon wafer having a thickness of 20 to 200 um (preferably from 30 to 150 um) is used.
The through-hole of the silicon substrate 10 is formed, for example, by photolithography or RIE (reactive ion etching).
The solid-state imaging device substrate 100 as a specific example of the embodiment above is described with reference to Fig. 1 and Fig. 2, but the embodiment above is not restricted to the configuration mode of Fig. 1 and Fig. 2, and the configuration of the device substrate is not particularly restricted as long as it is a configuration having a metal electrode and a light shielding film on the back surface side.
An example where the infrared ray shielding film obtained from the infrared ray shielding composition according to the invention is applied to a light shielding film of a wafer-level lens is described below with reference to the drawings.
Fig. 3 is a plan view showing one example of the wafer-level lens array having a plurality of wafer-level lenses.
As shown in Fig. 3, the wafer-level lens array comprises a substrate 410 and lenses 412 arrayed on the substrate 410. In Fig. 3, although a plurality of lenses 412 are two-dimensionally arrayed with respect to the substrate 410, they may be one-dimensionally arrayed.
Fig. 4 is a cross-sectional view along the line A-A in Fig. 3.
As shown in Fig. 4, in the wafer-level lens array, a light shielding film 414 for preventing light permeation from portions other than the lens 412 is provided between the plurality of lenses 412 arrayed on the substrate 410.
The wafer-level lens is composed of one lens 412 present on the substrate 410 and the light shielding film 414 provided in the circumferential edge part of the lens. The infrared ray shielding composition according to the invention is used for the formation of the light shielding film 414.
The configuration of a wafer-level lens array where a plurality of lenses 412 are two-dimensionally arrayed with respect to the substrate 410 as shown in Fig. 3 is described below as an example.
The lens 412 is ordinarily composed of the same material as the substrate 410 and is a lens integrally molded on the substrate 410 or a lens molded as a separate structure and fixed on the substrate. Although one example is described above, the wafer-level lens is not restricted to the embodiment and may take various embodiments, for example, a multilayer structure or a lens module separated by dicing.
Examples of the material for forming the lens 412 include glass. Since there is a wide variety of glass and glass having a high refractive index can be selected, the glass is suitable as a material for a lens intended to have a large power. Also, the glass is excellent in the heat resistance and has an advantage of withstanding the reflow mounting in an imaging unit or the like.
Other examples of the material for forming the lens 412 include a resin. The resin is excellent in the processability and suitable to simply and inexpensively form a lens face by using a mold or the like.
In this case, an energy curable resin is preferably used for the formation of the lens 412. The energy curable resin may be either a resin which is cured by heat or a resin which is cured by irradiation with an actinic energy ray (for example, irradiation with heat, an ultraviolet ray or an electron beam).
As to the energy curable resin, any known energy curable resin may be used and in consideration of reflow mounting in an imaging unit, a resin having a relatively high softening point, for example, a softening point of 200°C or more, is preferred and a resin having a softening point of 250°C or more is more preferred.
Examples
The invention is described below with reference to the examples, but the invention should not be construed as being limited thereto. Unless otherwise particularly indicated, all parts and percentages are on a weight basis.
Preparation of Filler dispersion 1>
Previously, 6.8 parts by weight of a silica filler (AEROSIL 50, produced by Nippon Aerosil Co., Ltd., particle size: 30 nm), 92.9 parts by weight of an alkali-soluble resin (ACA230AA, produced by Daicel-Cytec Co. Ltd., weight average molecular weight: 14,000 (value measured by a GPC method and calculated in terms of polystyrene), solid content: 50% by weight, solvent: PGME) and 0.3 parts by weight of melarnine were mixed and the mixture was dispersed in Motor Mill M-50 (produced by Eiger Ltd.) using zirconia beads having a diameter of 1.0 mm at a peripheral speed of 9 m/s for 1.5 hours to prepare Filler dispersion 1.
Preparation of Filler dispersion 2>
Figure imgf000096_0001
Previously, 92.9 parts by weight of a resin (weight average molecular weight: 10,000, solid content: 39% by weight, solvent: PGME) obtained by polymerization of monomers corresponding to the repeating units shown above respectively in a molar ratio of 65: 35, 6.8 parts by weight of a silica filler (AEROSIL 50, produced by Nippon Aerosil Co., Ltd., particle size: 30 nm) and 0.3 parts by weight of melarnine were mixed and the mixture was dispersed in Motor Mill M-50 (produced by Eiger Ltd.) using zirconia beads having a diameter of 1.0 mm at a peripheral speed of 9 m/s for 1.5 hours to prepare Filler dispersion 2.
Preparation of Infrared ray shielding composition>
Example 1
The compositions shown below were mixed and filtered to prepare an infrared ray shielding composition for Example 1. The solid state concentration of the infrared ray shielding composition for Example 1 was 47% by weight.
Light shielding particle: 18.5% by weight dispersion of YMF-02 19.13 parts by weight (produced by Sumitomo Metal Mining Co., Ltd., cesium tungsten oxide
(CS033WO 3), particle size which indicates a maximum value in a
particle size distribution: 20 nm)
Polymerizable compound: A-DCP (produced by Shin-Nakamura 4.63 parts by weight Chemical Co., Ltd., tricyclodecane dimethanol diacrylate (difunctional
polymerizable compound))
Triazine photopolymerization initiator: Compound A 1.10 parts by weight
Sensitizing agent: KAYACURE DETX-S (thioxanthone compound, 0.38 parts by weight produced by Nippon Kayaku Co., Ltd.)
Ultraviolet absorbing agent: DPO (produced by FUJIFILM 0.07 parts by weight Finechemicals Co., Ltd.)
Silane coupling agent: KBM-503 (produced by Shin-Etsu Silicone 2.10 parts by weight Co., Ltd.)
Surfactant: MEGAFAC F-780 (produced DIC Corp.) 0.10 parts by weight
Filler dispersion 1 shown above 58.39 parts by weig Solvent: PGMEA 14.10 parts
Figure imgf000097_0001
Compound A Compound B Compound C
Figure imgf000098_0001
Compound D Compound E
Examples 2 to 5
The infrared ray shielding compositions for Examples 2 to 5 were prepared in the same manner as in the infrared ray shielding composition for Example 1 except for replacing the triazine photopolymerization initiator (Compound A) with Compounds B to E, respectively. The solid state concentration of each of the infrared ray shielding compositions for Examples 2 to 5 was 47% by weight.
Example 6
The infrared ray shielding composition for Example 6 was prepared in the same manner as in the infrared ray shielding composition for Example 1 except that 58.39 parts by weight of Filler dispersion 1 was replaced with 72.10 parts by weight of Filler dispersion 2 and that the amount of PGMEA was changed from 14.10 pars by weight to 0.39 pars by weight. The solid state concentration of the infrared ray shielding composition for Example 6 was 43% by weight.
Examples 7 to 10
The infrared ray shielding compositions for Examples 7 to 10 were prepared in the same manner as in the infrared ray shielding composition for Example 6 except for replacing the triazine photopolymerization initiator (Compound A) with Compounds B to E, respectively. The solid state concentration of each of the infrared ray shielding compositions for Examples 7 to 10 was 43% by weight.
Comparative Example 1
The infrared ray shielding composition for Comparative Example 1 was prepared in the same manner as in the infrared ray shielding composition for Example 1 except for replacing the light shielding particle YMF-02 with the titanium black dispersion shown below. The solid state concentration of the infrared ray shielding composition for Comparative Example 1 was 47% by weight.
[Preparation of Titanium black dispersion]
(Production of Titanium black A) First, 100 g of titanium oxide having a particle size of 15 nm (MT-150A, produced by Tayca Corp.), 25 g of a silica particle having a BET surface area of 300 m2/g (AEROPERL 300/30, produced by Evonik Industries) and 100 g of DISPERBYK 190 (produced by BYK-Chemie GmbH) were weighed and thereto added 71 g of ion exchanged water. The resulting mixture was treated using a MAZERUSTAR KK-400W (produced by Kurabo Industries Ltd.) at an orbital rotation rate of 1,360 rpm and a spin rotation rate of 1,047 rpm for 20 minutes to obtain a uniform aqueous mixture. The aqueous mixture was charged into a quartz vessel and heated using a small rotary kiln (produced by Motoyama Co., Ltd.) under an oxygen atmosphere at 920°C. The atmosphere was substituted with nitrogen and then an ammonia gas was introduced at the same temperature as above at a rate of 100 irnVmin for 5 hours to conduct a nitrogen reduction treatment. After the treatment, the collected powder was ground in a mortar to obtain Titanium black A in the powder form.
(Synthesis of Dispersing agent 1)
Into a 500 ml three-necked flask were introduced 600.0 g of ε-caprolactone and 22.8 g of 2-ethyl-l-hexanol, and dissolved with stirring while blowing nitrogen gas. Then, 0.1 g of monobutyl tin oxide was added thereto, followed by heating to 100°C. After 8 hours, disappearance of the raw materials was confirmed by gas chromatography, and the mixture was cooled to 80°C. After adding 0.1 g of 2,6-di-tert-butyl-4-methylphenol thereto, 27.2 g of 2-methacryloyloxyethyl isocyanate was added thereto. After 5 hours, disappearance of the raw materials was confirmed by 1H-NMR, and the mixture was cooled to room temperature to obtain 200 g of Precursor Ml (having the structure shown below, n = 30) in the solid form. Identification mass spectrometry.
Figure imgf000099_0001
Precursor Ml
Into a three-necked flask substituted with nitrogen were introduced 30.0 g of Precursor Ml, 70.0 g of NK ESTER CB-1 (2- methacryloyloxyethyl phthalate, produced by Shin-Nakamura Chemical Co., Ltd.), 2.3 g of dodecyl mercaptan and 233.3 g of propylene glycol monomethyl ether acetate, and the mixture was stirred using a stirrer (THREE-ONE MOTOR, produced by SHINTO Scientific Co., Ltd.) and heated to 75°C while nitrogen was introduced into the flask. Then, 0.2 g of dimethyl 2,2-azobis(2-methyl propionate) (V-601, produced by Wako Pure Chemical Industries, Ltd.) was added thereto, followed by stirring with heating at 75°C for 2 hours. After 2 hours, 0.2 g of V-601 was further added, followed by stirring with heating for 3 hours to obtain a 30% by weight
Figure imgf000100_0001
n = 30
Dispersing agent 1
The composition ratio, acid value and weight average molecular weight (Mw) of Dispersing agent 1 were shown below. The weight average molecular weight was measured by gel permeation chromatography (GPC) and calculated in terms of polystyrene. The GPC was conducted using HLC-8020GPC (produced by Tosoh Corp.) with TSKGEL SUPER HZM-H, TSKGEL SUPER HZ4000 and TSKGEL SUPER HZ200 (produced by Tosoh Corp.) as columns. Composition ratio: x = 30% by weight, y = 70% by weight
Acid value: 80 mg KOH/g
Mw: 30,000
(Preparation of titanium black dispersion)
The components in Composition 1 shown below were mixed using a stirrer (EUROSTAR, produced by IKA Works, Inc.) for 15 minutes to obtain a dispersion.
(Composition 1)
Titanium black A produced above 25 parts by weight
Dispersing agent: Dispersing agent 1 prepared above (30% by weight 25 parts by weig solution)
Organic solvent: PGMEA 130 parts by weight
The dispersion thus obtained was subjected to a dispersion treatment under the conditions described below using an ULTRA APEX MILL UAM015 (produced by Kotobuki Industries Co., Ltd.) to obtain a titanium black dispersion (solid content concentration: 18.0% by weight). The particle size of titanium black dispersion indicating a maximum value in the particle size distribution was 19 nm.
(Dispersion conditions)
Bead size: φθ.05 mm
Bead filling ratio: 75% by volume
Mill peripheral speed: 8 m/sec
Amount of mixed solution to be dispersed: 500 g
Circulating flow rate (pump feed amount): 13 kg/hour
Temperature of treatment solution: 25 to 30°C
Cooling water: tap water
Volume of bead mill cyclic channel: 0.15 L
Number of passing: 90 passes
Comparative Example 2
The infrared ray shielding composition for Comparative Example 2 was prepared in the same manner as in the infrared ray shielding composition for Example 6 except for replacing the triazine polymerization initiator (Compound A) with an a-aminoketone polymerization initiator (IRGACURE 907, produced by BASF Japan Ltd.). The solid state concentration of the infrared ray shielding composition for Comparative Example 2 was 43% by weight.
<Evaluation of infrared ray shielding composition for solder resist>
(Evaluation of cracking)
Holes each having a diameter of 50 um and a depth of 70 μηι were formed in a silicon wafer, and a coating condition for forming a layer having a thickness of 30 um on the silicone wafer having no hole was determined. The infrared ray shielding composition described above was spin-coated under the condition determined above, and subjected to a pre-baking treatment at 100°C for 120 seconds, an ultraviolet curing treatment and a post-baking treatment at 150°C for one hour. The hole portion of the substrate thus-obtained was photographed using a crosssectional SEM and the presence or absence of cracking was visually evaluated. Ranking was conducted using five grades (5 to 1) based on the evaluation criteria shown below. The rank 4 or higher was considered to be acceptable.
[Evaluation criteria]
5: Level where 20 holes were observed and the presence of cracking was not recognized.
4: Level where 20 holes were observed and one cracking was recognized.
3: Level where 20 holes were observed and two crackings were recognized.
2: Level where 20 holes were observed and from 3 to 9 crackings were recognized and the presence of cracking could also be observed through a microscope from the above of the substrate.
1 : Level where 20 holes were observed and from 10 or more crackings were recognized and the presence of cracking could also be observed through a microscope from the above of the substrate. (Evaluation of adhesion property)
A coating condition for forming a layer having a thickness of 10 um on a silicone wafer was determined, and the infrared ray shielding composition described above was spin-coated under the condition determined above and subjected to a pre-baking treatment at 100°C for 120 seconds, an ultraviolet curing treatment and puddle development using an aqueous 2.38% by weight tetramethylammonium hydroxide solution at 25 °C for 40 seconds. Then, the substrate was rinsed with a spin shower, washed further with pure water and subjected to a post-baking treatment at 150°C for one hour. The substrate was allowed to stand under conditions of temperature of 110°C and humidity of 100% for 7 days, returned to room temperature (27°C), cut by a cutter to form 100 cross hatchings wherein the size of one cross hatching is 1 mm x 1 mm and a number of the cross hatchings which was not peeled off was counted. Ranking was conducted using five grades (5 to 1) based on the evaluation criteria shown below. The rank 3 or higher was considered to be acceptable.
[Evaluation criteria]
5: Level where neither peeling-off of the cross hatching nor chipped edge of the cross hatching was observed.
4: Level where no peeling-off of the cross hatching was observed but chipped edge of the cross hatching was observed in 1 to 10 cross hatchings.
3: Level where no peeling-off of the cross hatching was observed but chipped edge of the cross hatching was observed in 11 to 100 cross hatchings.
2: Level where peeling-off of the cross hatching was observed.
1 : Level where all of cross hatchings was peeled off.
(Singe entire surface exposure sensitivity (layer exposure sensitivity) of solder resist)
Each of the infrared ray shielding compositions for Examples 1 to 10 and Comparative Examples 1 and 2 was coated on a silicone wafer by a spin coating method so as to have a layer thickness of 25 um and dried on a hot plate at 120°C for 2 minutes to obtain a photosensitive layer.
The photosensitive layer was subjected to single entire surface exposure using an i-line exposure device in an amount of 1,000 mJ. The exposed photosensitive layer was subjected to puddle development using N-methyl-2-pyrrolidone (NMP) at 25°C for 40 seconds, rinsed with a spin shower and washed further with pure water. A rate of the layer thickness after the rinsing to that of after the exposure (rate of thickness decrease) was determined and evaluated according to the criteria shown below.
[Evaluation criteria]
5: The rate of thickness decrease was not more than 5%.
4: The rate of thickness decrease was 5% or more but not more than 10%.
3: The rate of thickness decrease was 10% or more but not more than 20%.
2: The rate of thickness decrease was 20% or more but not more than 30%.
1 : The rate of thickness decrease was more than 30%.
(Formation of solder resist pattern)
As to the infrared ray shielding compositions for Examples 1 to 5 and Comparative Example 1, pattern formation was conducted.
Specifically, each of the infrared ray shielding compositions for Examples 1 to 5 and Comparative Example 1 was coated on a silicone wafer by a spin coating method so as to have a layer thickness of 25 um and dried on a hot plate at 120°C for 2 minutes to obtain a photosensitive layer.
Then, the photosensitive layer was irradiated using an i-line stepper through a photomask containing a circular pattern having a diameter of 300 um with changing an exposure amount in steps of 50 mJ/cm in a range from 50 to 2,000 mJ/cm .
The exposed photosensitive layer was subjected to puddle development using an aqueous 2.38% by weight tetramethylammonium hydroxide solution at 25°C for 60 seconds, rinsed with a spin shower and washed further with pure water to obtain an infrared ray shielding solder resist pattern. A minimum exposure amount (mJ/cm2) for obtaining a circle pattern having a diameter of 300 μπι when the development step was conducted for 60 seconds (pattern exposure sensitivity) was measured. As the numerical value is smaller, the pattern exposure sensitivity is better. The evaluation was conducted according to the criteria shown below.
[Evaluation criteria]
5: The minimum exposure amount was not more than 200 mJ/cm2.
4: The minimum exposure amount was more than 200 mJ/cm2 but not more than 250 mJ/cm2.
3: The minimum exposure amount was more than 250 mJ/cm2 but not more than 300 mJ/cm2.
2: The minimum exposure amount was more than 300 mJ/cm2 but not more than 350 mJ/cm2.
1 : The minimum exposure amount was more than 350 mJ/cm2.
(Evaluation of pattern profile)
According to the above (Formation of solder resist pattern), the exposure with the minimum exposure amount and development were conducted to form a pattern. A profile of the pattern was evaluated according to the criteria shown below.
[Evaluation criteria]
5: The pattern was formed on the substrate with sufficient adhesion property and the cross-section of the pattern showed a good rectangular shape.
4: The pattern was formed on the substrate with sufficient adhesion property but the cross-section of the pattern did not show a good rectangular shape.
3: The pattern was formed on the substrate with sufficient adhesion property but the cross-section of the pattern had an undercut profile and did not show a rectangular shape.
2: A kind of a pattern was formed but the adhesion properly to the substrate was insufficient and a pattern stably adhering on the substrate could not be formed.
1 : A pattern could not be resolved.
(Evaluations of infrared ray shielding property and visible light transparence)
The infrared ray shielding composition was spin-coated on a glass substrate under the conditions described above to form a coating of a photosensitive layer having a layer thickness of 25 urn and the transmittance at a wavelength of 1,200 nm of the coating was measured using UV-VIS-NIR Spectrophotometer UV-3600 (produced by Shimadzu Corp.). As the transmittance is smaller, the infrared shielding property is more excellent. The evaluation was conducted according to the criteria shown below.
[Evaluation criteria]
5: The transmittance is not more than 2%.
4: The transmittance is more than 2% but not more than 3%.
3: The transmittance is more than 3% but not more than 5%.
2: The transmittance is more than 5% but not more than 10%.
1 : The transmittance is more than 10%.
Further, the transmittance at a wavelength of 550 nm of the coating was measured using UV-VIS-NIR Spectrophotometer UV-3600 (produced by Shimadzu Corp.). As the numerical value is larger, the visible light transparence is more excellent. The evaluation was conducted according to the criteria shown below.
[Evaluation criteria]
5: The transmittance is not less than 30%.
4: The transmittance is less than 30% but not less than 25%.
3: The transmittance is less than 25% but not less than 20%.
2: The transmittance is less than 20% but not less than 15%.
1 : The transmittance is less than 15%. The results of the evaluations are shown in Table 1 below.
TABLE 1
Figure imgf000106_0001
As is apparent from the results shown in Table 1, Comparative Example 1 using titanium black as the infrared ray shielding agent exhibits the occurrence of many crackings, is inferior in the adhesion property to the substrate and film exposure sensitivity, and, in particular, is extremely inferior in the visible light transparence. It is also found that in the case of the pattern formation, Comparative Example 1 is inferior in the pattern exposure sensitivity and pattern profile.
On the contrary, it can be seen that Examples 1 to 5 using the cesium tungsten oxide particle as the infrared ray shielding agent and the triazine polymerization initiator exhibit no or small occurrence of cracking and are excellent in any of the adhesion property to the substrate, film exposure sensitivity, infrared ray shielding property and visible light transparence. It is also found that in the case of the pattern formation, Examples 1 to 5 are excellent in the pattern exposure sensitivity and pattern profile.
It can be seen that Comparative Example 2 using the cesium tungsten oxide particle as the infrared ray shielding agent and the polymerization initiator other than the triazine polymerization initiator is excellent or in the acceptable level in the adhesion property to the substrate, infrared ray shielding property and visible light transparence, but is inferior in the occurrence of cracking and film exposure sensitivity.
On the contrary, it can be seen that Examples 6 to 10 using the cesium tungsten oxide particle as the infrared ray shielding agent and the triazine polymerization initiator exhibit no or small occurrence of cracking, are in the acceptable level in the adhesion property to the substrate and are excellent in any of the film exposure sensitivity, infrared ray shielding property and visible light transparence.
This application is based on Japanese Patent application JP 2011-253228, filed on November 18, 2011, the entire content of which is hereby incorporated by reference, the same as if fully set forth herein.

Claims

1. An infrared ray shielding composition comprising a fine particle of tungsten oxide containing an alkali metal, a triazine polymerization initiator and a polymerizable compound.
2. The infrared ray shielding composition as claimed in Claim 1, wherein the triazine
Figure imgf000108_0001
hydrogen atom, a halogen atom, a dialkylamino group, an alkyl group, an alkoxy group or a cyano group; Y1 represents an ethenylene group or an -NH- group; B1 and B2 each independently represents an aromatic ring group which may have a substituent; and 1 and m each independently represents any integer selected from 0, 1 and 2.
3. The infrared ray shielding composition as claimed in Claim 2, wherein X1 and X2 in the formula (T) each independently represents a halogen-substituted hydrocarbon group.
4. The infrared ray shielding composition as claimed in Claim 2 or 3, wherein an aromatic
1 2
ring constituting the aromatic ring group for B or B in the formula (T) is a benzene ring.
5. The infrared ray shielding composition as claimed in any one of Claims 1 to 4, which further comprises an alkali-soluble binder.
6. The infrared ray shielding composition as claimed in Claim 5, wherein the alkali-soluble binder has an acid group.
7. The infrared ray shielding composition as claimed in Claim 5 or 6, wherein the alkali-soluble binder has a crosslinkable group.
8. The infrared ray shielding composition as claimed in any one of Claims 1 to 7, wherein the fine particle of tungsten oxide containing an alkali metal is represented by the following formula (I):
MxWyOz (I)
wherein M represents an alkali metal; W represents tungsten; O represents oxygen; 0.001 < x/y < l.l; and 2.2 < z/y < 3.0.
9. The infrared ray shielding composition as claimed in any one of Claims 1 to 8, wherein the polymerizable compound is a polyfunctional polymerizable compound having a plurality of polymerizable groups in a molecule of the polyfunctional polymerizable compound.
10. The infrared ray shielding composition as claimed in any one of Claims 1 to 9, which is used for a solder resist or an infrared ray shielding film on a rear side of a silicon substrate in a solid-state imaging device.
11. A photosensitive layer, which is formed from the infrared ray shielding composition as claimed in any one of Claims 1 to 10.
12. An infrared ray shielding film, which is formed from the infrared ray shielding composition as claimed in any one of Claims 1 to 10.
13. A solid-state imaging device comprising a substrate having an imaging device unit formed on one surface of the substrate, and the infrared ray shielding film as claimed in Claim 12 provided on the other surface side of the substrate.
14. A pattern forming method comprising, in the following order:
forming the photosensitive layer as claimed in Claim 11 ;
pattern-exposing the photosensitive layer to cure an exposed area; and
removing an unexposed area by alkali development to form a pattern.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016010593A1 (en) * 2014-07-16 2016-01-21 Eye Ojo Corporation Methods and system for manufacturing infrared (ir) absorbing lens
CN107406707A (en) * 2015-01-27 2017-11-28 住友金属矿山株式会社 Near-infrared absorbing particle dispersion liquid and its manufacture method

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6077952B2 (en) * 2013-07-01 2017-02-08 富士フイルム株式会社 Near-infrared absorbing composition, near-infrared cut filter and manufacturing method thereof, and camera module and manufacturing method thereof
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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005037881A (en) * 2003-04-21 2005-02-10 Fuji Photo Film Co Ltd Pattern forming method, image forming method, fine particle adsorption pattern forming method, conductive pattern forming method, pattern forming material, and planographic printing plate
JP2006084872A (en) * 2004-09-16 2006-03-30 Fuji Photo Film Co Ltd Polymerizable composition and image recording material using same
WO2009020207A1 (en) * 2007-08-09 2009-02-12 Dai Nippon Printing Co., Ltd. Near infrared absorbing composition and near infrared absorbing filter
JP2009062409A (en) * 2007-09-04 2009-03-26 Bridgestone Corp Near infrared-shielding material, laminate and optical filter for display using the same and display
JP2009205029A (en) * 2008-02-29 2009-09-10 Dainippon Printing Co Ltd Near-infrared light absorbing material
JP2009230094A (en) * 2007-07-03 2009-10-08 Fujifilm Corp Light shielding member, method of manufacturing light shielding member, ultraviolet absorbing film, infrared absorbing film, photomask, and electromagnetic wave shielding film
JP2010008818A (en) * 2008-06-27 2010-01-14 Sumitomo Metal Mining Co Ltd Near infrared ray absorption filter for plasma display panel, and plasma display panel
JP2010113044A (en) * 2008-11-05 2010-05-20 Okamoto Kagaku Kogyo Kk Photosensitive composition and negative lithographic printing plate precursor using the same
JP2011053348A (en) * 2009-08-31 2011-03-17 Okamoto Kagaku Kogyo Kk Composition for forming protective layer, and lithographic printing plate precursor using the same

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005037881A (en) * 2003-04-21 2005-02-10 Fuji Photo Film Co Ltd Pattern forming method, image forming method, fine particle adsorption pattern forming method, conductive pattern forming method, pattern forming material, and planographic printing plate
JP2006084872A (en) * 2004-09-16 2006-03-30 Fuji Photo Film Co Ltd Polymerizable composition and image recording material using same
JP2009230094A (en) * 2007-07-03 2009-10-08 Fujifilm Corp Light shielding member, method of manufacturing light shielding member, ultraviolet absorbing film, infrared absorbing film, photomask, and electromagnetic wave shielding film
WO2009020207A1 (en) * 2007-08-09 2009-02-12 Dai Nippon Printing Co., Ltd. Near infrared absorbing composition and near infrared absorbing filter
JP2009062409A (en) * 2007-09-04 2009-03-26 Bridgestone Corp Near infrared-shielding material, laminate and optical filter for display using the same and display
JP2009205029A (en) * 2008-02-29 2009-09-10 Dainippon Printing Co Ltd Near-infrared light absorbing material
JP2010008818A (en) * 2008-06-27 2010-01-14 Sumitomo Metal Mining Co Ltd Near infrared ray absorption filter for plasma display panel, and plasma display panel
JP2010113044A (en) * 2008-11-05 2010-05-20 Okamoto Kagaku Kogyo Kk Photosensitive composition and negative lithographic printing plate precursor using the same
JP2011053348A (en) * 2009-08-31 2011-03-17 Okamoto Kagaku Kogyo Kk Composition for forming protective layer, and lithographic printing plate precursor using the same

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016010593A1 (en) * 2014-07-16 2016-01-21 Eye Ojo Corporation Methods and system for manufacturing infrared (ir) absorbing lens
CN107406707A (en) * 2015-01-27 2017-11-28 住友金属矿山株式会社 Near-infrared absorbing particle dispersion liquid and its manufacture method
CN107406707B (en) * 2015-01-27 2021-02-19 住友金属矿山株式会社 Near-infrared-absorbing microparticle dispersion and method for producing same

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